CN1260829A - Photobleaching compositions comprising mixed metallocyanines - Google Patents
Photobleaching compositions comprising mixed metallocyanines Download PDFInfo
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- CN1260829A CN1260829A CN98803338A CN98803338A CN1260829A CN 1260829 A CN1260829 A CN 1260829A CN 98803338 A CN98803338 A CN 98803338A CN 98803338 A CN98803338 A CN 98803338A CN 1260829 A CN1260829 A CN 1260829A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating compounds
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- Detergent Compositions (AREA)
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Abstract
The present invention relates to hybrid metallocyanine ring photosensitizers and mixtures thereof useful in laundry detergent compositions as low hue photobleaches. The hybrid rings are formed from suitable aromatic rings, inter alia, benzene, 1,2-naphthalene, and 2,3-naphthalene. The present invention also relates to conpositions for cleaning and disinfecting hard surfaces. The present invention further relates to methods for photobleaching fabrics and to methods for disinfecting hard surfaces.
Description
The field of the invention
The present invention relates to can be used in the laundry detergent composition hybridized metal cyanines photosensitizers and its mixture as the low key tone optical white.The invention still further relates to the composition that is used to wash with disinfecting hard surfaces.The invention further relates to methods for photobleaching fabrics and methods for disinfecting hard surfaces.
Background technology of the present invention
Known some water soluble metal phthalocyanine, naphthalene cyanines and metal cyanine compound can be used as optical white and bacteriostatic agent.Phthalocyanine and naphthalene cyanines or their metal complexes can form " singlet oxygen ", and promptly a kind of can the reaction with stain bleached into colourless it and the oxidizing substance of water-soluble state normally.
The example of existing many phthalocyanines and naphthalene cyanines optical white, the most frequently used is Phthalocyanine Zinc and aluminum phthalocyanine.In the literature, said " photosensitizers " is commonly used to substitute " light activating agent ", and this term of back that therefore is considered to be equivalent to whole specification sheets all the time and is adopted.
Prior art points out to have the phthalocyanine and the naphthalene cyanine compound of following general formula
Wherein Me is transition metal or nontransition metal, (Sens.) be phthalocyanine or naphthalene cyanines ring, it is when suitable Me unit combines, can carry out the photosensitization of oxygen molecule, the R unit is a substituting group, and it is connected on the photosensitization ring element (Sens.), improves the solvability or the spectrochemical property of molecule, the Y unit is the substituting group that is connected with atoms metal, and the negatively charged ion of neutral charge for example is provided.The specific substituent R unit that selection is used to substitute onto on the molecule has been the emphasis of studying for many years, and these unit are generally selected by formulator, makes to reach required water-soluble in the molecules of interest.
The major limitation that uses phthalocyanine and naphthalene cyanine compound to be used for the fabric photobleaching is that these molecules are dark matters.The Q band of phthalocyanine is absorbed in the scope of 600～700 nanometers, and the Q of naphthalene cyanines band is absorbed in the scope of 700～800 nanometers.
In general, the cyanines ring is to be formed by four " monomeric units " that form big cyanines ring that react.For example, four times m-dicyanobenzene one reacts, and forms the unsubstituted cyanines ring that is known as phthalocyanine.Be defined as the cyanines ring of " homogeneous " in purpose of the present invention by the cyanines cyclic group of four identical " monomeric units " formations.Character with non-hydridization cyanines homogeneous many replacements are that prior art is known.
The mixture of unexpectedly finding " hydridization cyanines and hybridized metal cyanines " and hydridization cyanines and metal cyanines now produces singlet oxygen, therefore can play the effect of optical white or light sterilizing agent.These " hydridization cyanines and metal cyanines " have and are not the cyanines ring that all is made of four identical monomers.For example, this monomeric unit can contain replace or all of unsubstituted benzene, naphthalene, anthracene or phenanthrene ring in conjunction with as A, B, C or D in the general formula below.
Common photobleaching material has narrow strong Q band and absorbs.On the contrary, blended cyanines of the present invention and metal cyanines have wide, not too strong Q band and absorb, and this has reduced the color of photobleaching.
The present invention also provides hybridized metal cyanines and its mixture of axial replacement, and they have the high-level efficiency of formation singlet oxygen and required solvability and weather resistance.The change of the character of the metal cyanines ring that these axially replace is with axially group is irrelevant.This description and selectively changing help the ability of key structure element of the destination properties of this molecule to make formulator to carry out according to the rule of " hit and lose " (" hit and miss ").
The hybridized metal cyanines photosensitizers mixture that the purpose of this invention is to provide " competent " and " not durable "." competent " metal cyanines photosensitizers attracts from the teeth outwards, and " non-resistant " metal cyanines photosensitizers rejects the surface.
Another object of the present invention provides the durable and non-resistant photobleaching laundry composition that is used for natural, synthetic or mixed goods.
A further object of the invention provides the bleaching composition that contains non-water and low water carrier, and promptly photo bleach compositions contains wherein half following carrier of water formation carrier liq.
A further object of the invention provides and is used for the imporosity crust, and particularly Formica , ceramic tile, glass or be used for the porousness crust are as the durable and non-competent photobleaching hard-surface cleaning compositions of concrete or timber.
An object of the present invention is to provide the method that laundry composition that a kind of employing contains hybridized metal cyanines optical white of the present invention comes bleached woven fabric.
An object of the present invention is to provide the method that composition that a kind of employing contains hybridized metal cyanines optical white of the present invention comes cleaning of hard surfaces.
Background technology
Many patent documentations all relate to the purposes and their preparation and synthetic of photochemical bleaching or phthalocyanine and naphthalene cyanine compound.Referring to for example US3094536, obtained power on June 18th, 1963; US3927967 obtained power on December 23rd, 1975; US4033718 obtained power on July 5th, 1977; US4166718 obtained power on September 4th, 1979; US4240920 obtained power on December 23rd, 1980; US4255273 obtained power on March 10th, 1981; US4256597 obtained power on March 17th, 1981; US4318883 obtains power March 9 nineteen eighty-two; US4368053 obtains power January 11 nineteen eighty-three; US4497741 obtained power on February 5th, 1985; US4648992 obtained power on March 10th, 1987; And UK1372035, on October 30th, 1974 is open; UK1408144, on October 1st, 1975 is open; UK2159516, on December 4th, 1985 is open; EP381211A2, August 8 nineteen ninety is open; EP484027A1, on May 6th, 1992 is open; WO91/18006, on November 28th, 1991 an open and day disclosure 06-73397 Derwent summary No. (94-128933), on March 15th, 1994 is open.
Except above-mentioned patent documentation, other document of having put down in writing synthetic, the preparation of phthalocyanine and naphthols and character is in the present invention in conjunction with having as a reference: phthalocyanine: Properties andApplications, Leznoff, C.C.and Lever A B.P. (Eds), VCH, 1989; Infrared Absorbing Dyes, Matsuoka, M. (Ed), Plenum, 1990; Inorg.Chem., Lowery, M.J.et al., 4, pg.128, (1965); Inorg.Chem., Joyner, R.D.et al., 1, pg.236, (1962); Ingor.Chem., Kroenke, W.E.et al., 3696,1964; Ingor.Chem.Esposito, J.N.etal., 5, pg.1979, (1966); J.Am Chem.Soc.Wheeler, B.L.et al., 106, pg.7404, (1984); Ingor.Chem.Ford, W.E.et al., 31, pg.3371, (1992); Material Science, Witkiewicz, Z.et al., 11, pg.39, (1978); J.Chem.Soc.Perkin Trans.I, Cook, M.J., et al., pg.2453, (1988).
Summary of the present invention
The present invention relates to hybridized metal cyanines photosensitive mixtures, this mixture contains one or several hydridization light-sensitive compounds, and the general formula of every kind of compound is:
Wherein each metal cyanines of mixture contain:
A) photolytic activity metal or nonmetal M, wherein said photolytic activity metal or nonmetal M are selected from silicon, germanium, tin, lead, aluminium, platinum, palladium, phosphorus and their mixture, and condition is that said metal or nonmetallic valency are 3 or 4;
B) aromatic nucleus A, B, C and D, wherein each ring be selected from replacement respectively or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, anthracene, phenanthrene and their mixture; With
C) the axial R unit of adjusting solubleness and weather resistance; The value of t is 1 or 2;
Condition is that the Q band maximum absorption wavelength scope of every kind of photosensitizers of said mixture is 600 nanometers or bigger.
The light-sensitive compound of the present invention's record is applicable to laundry detergent composition and light sanitizing composition.
Another object of the present invention provide can be effectively as the photo bleach compositions of detergent for washing clothes additive.
A further object of the invention provides a kind of method that contacts clean textile by the fabric that will need to clean and photo bleach compositions of the present invention.
All percentage ratios of the present invention, ratio and proportioning all are weight, unless other explanation is arranged.All temperature all be degree centigrade (℃), unless other explanation is arranged.The file relevant portion of all references is all in conjunction with in the present invention as a reference.
Detailed description of the present invention
The cleaning compositions of disinfecting hard surfaces effectively of the present invention or fabric contains:
A) at least about 0.001ppm, preferred 0.005 to 2000ppm, more preferably 0.1 to 1000ppm hybridized metal cyanines photosensitive mixtures, and this mixture contains one or several, preferred about 3 kinds to about 100 kinds, more preferably from about 10 kinds are arrived about 100 kinds of hybrid compounds of the present invention; With
B) balance carrier and additive materials.
The laundry detergent composition that is effective to clean textile of the present invention contains:
A) at least about 0.1%, preferred about 0.1% to about 95%, more preferably from about 0.1% to the detergent surfactant of about 30% weight, and said tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture;
B) at least about 0.001ppm, preferred 0.005 arrives 2000ppm, more preferably 0.1 to 1000ppm hydridization cyanines optical white of the present invention; With
C) balance carrier and additive materials.
Preferred laundry detergent composition of the present invention contains:
A) at least about 0.1%, preferred about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to the detergent surfactant of about 20% weight, and said detergent surfactant is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture;
B) at least about 0.001ppm, preferred about 0.01 arrives 10000ppm, more preferably from about 0.1 arrives about 5000ppm, most preferably from about 10 to 1000ppm hydridization cyanines optical white of the present invention;
C) at least about the stain remover of 0.01% weight; With
D) carrier and additive materials.
The preferred laundry detergent composition of another kind of the present invention contains:
A) at least about 0.1%, preferred about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to the detergent surfactant of about 20% weight, and said detergent surfactant is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture;
B) at least about 0.001ppm, preferred about 0.01 arrives 10000ppm, more preferably from about 0.1 arrives about 5000ppm, most preferably from about 10 to 1000ppm hydridization cyanines optical white of the present invention;
C) at least about the Halogen SYNTHETIC OPTICAL WHITNER of 0.01% weight; With
D) carrier and additive materials.
The preferred laundry detergent composition of another kind of the present invention contains:
A) at least about 0.1%, preferred about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to the detergent surfactant of about 20% weight, and said detergent surfactant is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture;
B) at least about 0.001ppm, preferred about 0.01 arrives 10000ppm, more preferably from about 0.1 arrives about 5000ppm, most preferably from about 10 to 1000ppm hydridization cyanines optical white of the present invention;
C) at least about the modified polyamine dispersion agent of 0.01% weight; With
D) carrier and additive materials.
In order to reach purpose of the present invention, the aryl unit of replacement is the part with following general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganics comprises sulfate radical, bisulfate ion, phosphate radical etc.
Based on purpose of the present invention, the alkylidene aryl unit is the part with following general formula:
R wherein
34And R
35As mentioned above, p is 1 to about 10.Based on purpose of the present invention, the aryloxy unit is the part with following general formula;
R wherein
34And R
35As mentioned above.Based on purpose of the present invention, the alkylene oxide group aryl unit is the part with following general formula:
R wherein
34And R
35As mentioned above, q is 0 to about 10.Based on purpose of the present invention, the oxyalkylene aryl unit is the part with following general formula:
R wherein
34And R
35As mentioned above, w is 1 to about 10.Based on purpose of the present invention, the oxyalkyl units of collateralization is the part with following general formula:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H, OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; Preferred C
1-C
18Alkyl ,-CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M, preferred-SO
3 -M
+,-OSO
3 -M
+M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively, and z can have 0 to 100 value respectively.
Based on purpose of the present invention, what replace has aforesaid coefficient p, q and w with unsubstituted aryl, alkylidene aryl, aryloxy, oxyalkylene aryl and alkylene oxide group aryl, aryl can be any being substituted or unsubstituted aromatic portion, comprise heterocycle, for example phenyl, naphthyl, thienyl, pyridyl etc.
Based on purpose of the present invention, alkyl ethyleneoxy group unit is the part with following general formula:
-(A)
k-(CH
2)
m(OCH
2CH
2)
nZ wherein A is heteroatoms nitrogen or oxygen, and preferred A is an oxygen, and when not having heteroatoms, k is 0, and when heteroatoms was arranged, k equaled 1, and Z is a hydrogen, C
1-C
6Alkoxyl group, the aryloxy of the aryl of aryl, replacement, aryloxy, replacement, alkylidene amino ,-SO
3 -M
+,-OSO
3 -M
+,-CO
2H and their mixture; M is 0 to 12, and n is 1 to 100.
Based on purpose of the present invention, the alkylidene amino unit is the part with following general formula:
R wherein
26And R
27Be C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, R
28Be hydrogen, C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization and their mixture, A is heteroatoms nitrogen or oxygen, and preferred A is an oxygen, and when not having heteroatoms, v is 0, and when heteroatoms was arranged, v equaled 1, and X is chlorine, bromine, iodine or other water soluble anion, and u is 0 to 22.Other water soluble anion example comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.
Hydridization cyanines ring
Be suitable for containing hydridization cyanines ring as the photosensitizers of the present invention of optical white and light sterilizing agent.These hydridization rings are to form by at least two kinds of fragrant monomer unit one react withs that can form a cyanines ring.In general, the cyanines ring depends on the unitary type of fragrant monomer that is used for synthetic required big ring, and for example phthalocyanine is that derivative by benzene forms, and the naphthalene cyanines are to be formed by naphthalene derivatives etc.
Hydridization cyanines of the present invention have following general formula:
Wherein A, B, C and D represent aromatic nucleus.Based on purpose of the present invention, benzene that these aromatic nucleus preferably replace or unsubstituted, 1,2-naphthylidene, 2,3-naphthylidene, anthracene and phenanthrene.But listed is not other qualification or eliminating that can be incorporated into the aromatic nucleus on the cyanines ring to all.
Cyanines ring of the present invention is to be formed by two kinds or several different monomer.These monomers are difference aspect the type of encircling replacement type, the geometric configuration that encircles substituent, aromatic nucleus or their mixture.In general, the fragrant dicyano compound of ortho position replacement is the suitable feedstock that is used for the cyanines ring.But, the present invention includes the method that all are applicable to preparation heterocycle cyanine compound and their mixture.
Based on further describing purpose of the present invention, following general formula has been described when the monomer that forms the cyanines ring, 1,6-dimethoxy-3,4-dicyanobenzenes and 1,6-two bromo-3, the 4-dicyanobenzenes, the mixture that is contemplated to of the cyanines ring that next reacts prepared in appropriate condition.
Reaction generates under appropriate condition:
Other example includes, but are not limited to adjacent dicyanobenzenes and 2, and the 3-dicyano naphthalene carries out reaction as follows:
Perhaps carry out following reaction with corresponding phthalimidine:
Generate the mixture of hydridization cyanines I-VI as follows.
Other example includes, but are not limited to 1,4-dibutoxy-2, and 3-dicyanobenzenes and 2, the 3-dicyano naphthalene carries out reaction as described below:
The mixture of hydridization cyanines I-VI shown in below generating:
The mixture of the material that said " hydridization cyanines " generate when comprising two kinds or more of monomer reaction.Skilled in the art will recognize that this mixture contains non-hybrid structure, non-hybrid structure has fallen in the scope based on " the hydridization cyanines " of the object of the invention.Also know the increase along with the different monomers number, the possible hydridization ring that is produced and the number of non-hydridization ring also increase.
As mentioned above, " hydridization cyanines " can be formed by several monomers.In addition, can change these monomeric stoichiometric ratios.List the indefiniteness example that generates the reaction that mixes cyanines below.
Wherein the ratio of x and y is represented the stoichiometry of every kind of reactant, and said reactant ratio is in 0.01 to 100 scope, and promptly when the value of y was 100, the value of x can be 1, and when the value of y was 1, the value of x can be 100.Following general formula:
Be primary product by following reactive chemistry metering:
Based on purpose of the present invention, can be write as any one of following two equivalence resonance general formulas by the ring component that generates with unsubstituting phenenyl that replaces:
Or
R wherein
1, R
2, R
3And R
4Be selected from following substituting group respectively.
Based on purpose of the present invention, by replace with unsubstituted 2, the ring component that the 3-naphthalene produces can be write as any one of following two equivalence resonance general formulas:
Or
R wherein
1, R
2, R
3, R
4, R
5And R
6Be selected from following substituting group respectively.
Based on purpose of the present invention, by replace with unsubstituted 1, the ring component that the 2-naphthylidene produces can be write as any one of following two equivalence resonance general formulas:
Or
R wherein
1, R
2, R
3, R
4, R
5And R
6The unit is selected from following substituting group respectively.
Based on purpose of the present invention, can be write as any one of following two equivalence resonance general formulas by the ring component that replaces with unsubstituted anthracene generation:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit is selected from following substituting group respectively.
Based on purpose of the present invention, can be write as any one of following two equivalence resonance general formulas by the ring component that replaces with unsubstituted luxuriant and rich with fragrance generation:
Or
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit is selected from following substituting group respectively.
The aromatic nucleus substituting group
Hydridization cyanines of the present invention can be that replace or unsubstituted, i.e. R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit contains:
A) hydrogen;
B) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
G) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) C of poly-hydroxy replacement
3-C
22Alkyl;
I) C
1-C
22Alkoxyl group, preferred C
1-C
4Alkoxyl group, more preferably methoxyl group;
J) alkoxyl group of collateralization, general formula is as follows:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H, OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively, preferred 0 to 6; Z can have 0 to 100 value respectively, and preferred 0 to about 10, and more preferably 0 to about 3;
K) following aryl and the substituted aryl of general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl, CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, other parts are C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.;
L) have the alkylidene aryl of following general formula and the alkylidene aryl of replacement
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; P is 1 to about 10, preferred 1 to about 3;
M) have the aryloxy and the substituted aryloxy of following general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.;
N) the alkylene oxide group arylalkyleneoxy aryl unit of alkylene oxide group aryl and replacement is the part with following general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; Q is 0 to about 10, preferred about 1 to about 3;
O) have the oxyalkylene aryl of following general formula and the oxyalkylene aryl of replacement:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; W is 1 to about 10, preferred about 1 to about 3;
P) C
1-C
22Alkylthio, C
3-C
22Alkylthio that replaces and their mixture;
Q) ester units, general formula is-CO
2R
25, R wherein
25Be C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, all these all replace with halogen; The C that poly-hydroxy replaces
3-C
22Alkyl, C
3-C
22Glycol; C
1-C
22Alkoxyl group, C
3-C
22The alkoxyl group of collateralization; The aryl of aryl, replacement, alkylidene aryl, aryloxy, alkylene oxide group aryl, alkylene oxide group aryl; Preferred C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization and their mixture;
R) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be respectively C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl, R
28Be hydrogen, C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization and their mixture, A is heteroatoms nitrogen or oxygen, preferred A is an oxygen, when not having heteroatoms, v equals 0, and when heteroatoms was arranged, v equaled 1, and preferred v is 0, X is chlorine, bromine, iodine or other water soluble anion, and u is 0 to 22, and preferred u is 3 to about 10.Other water soluble anion example comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.
S) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Contain C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl and their mixture;
T) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
k-(CH
2)
m(OCH
2CH
2)
nZ
A is nitrogen or oxygen, and preferred A is an oxygen, and when not having heteroatoms, k is 0, and when heteroatoms was arranged, k equaled 1, and Z is hydrogen, C
1-C
6The aryloxy of the aryl of alkoxyl group, aryl, replacement, aryloxy, replacement, alkylidene amino ,-SO
3 -M
+,-OSO
3 -M
+,-CO
2H and their mixture, preferred hydrogen or C
1-C
6Alkoxyl group, more preferably methoxyl group; N is 1 to 100, and preferred 0 to about 20, more preferably 3 to about 10; M is 1 to 12, preferred about 1 to about 5;
U) following siloxy-and the siloxy-of the replacement :-OSiR of general formula
31R
32R
33, R wherein
31, R
32And R
33Be selected from C respectively
1-C
8Alkyl, C
3-C
8The alkyl of collateralization, C
2-C
8Alkenyl, C
3-C
8The alkenyl of collateralization, the alkyl of replacement, aryl, alkyl inferior ethoxyl unit, its general formula is:
-(A)
k-(CH
2)
m(OCH
2CH
2)
nZ wherein Z is hydrogen, C
1-C
30Alkyl, hydroxyl ,-CO
2H ,-SO
3 -M
+,-OSO
3 -M
+, C
1-C
6The aryloxy of the aryl of alkoxyl group, aryl, replacement, aryloxy, replacement, alkylidene amino and their mixture; A contains the unit nitrogen or oxygen, and M is a water-soluble cationic, and k is 0 or 1, and n from 0 to 100, and m is 0 to 12; And their mixture; With alkylidene amino unit and their mixture.
Preferred aromatic nucleus substituting group is hydrogen, halogen and their mixture, preferred chlorine, bromine, iodine and their mixture, more preferably bromine; C
1-C
22Alkoxyl group, preferred C
1-C
4Alkoxyl group, more preferably methoxyl group; That replace or unsubstituted aryloxy, preferably unsubstituted, the sulfonate radical of replacement or carboxylate radical; C
1-C
6The alkyl of linearity or collateralization; And C
2-C
6The alkenyl of linearity or collateralization.
Metal and non-metallic atom
Cyanines ring of the present invention can be randomly and suitable metal-chelating.All photolytic activity metals or nonmetal all being applicable to as by the central atom of cyanines ring chelating.Preferred metal and nonmetal be zinc, silicon, germanium, tin, lead, aluminium, platinum, palladium and phosphorus, more preferably silicon, tin and germanium.
Be to be combined with the metal of cyanines ring or the example of non-metallic atom below:
Wherein central atom contains the Si with hydridization cyanines ring chelating
4+Atom.Hydridization ring of the present invention occupies each metal that is chelated or nonmetallic two valencys.In above-mentioned example, the Siliciumatom of tetravalence (4+) is by phthalocyanine ring chelating.Two silicon valencys are chelated and occupy, and remaining valency is used for being connected with " axially R unit " simultaneously.Not all being applicable to as photolytic activity metal or nonmetallic central atom all has tetravalence.For example, the valency of aluminium atom is three (3+).Therefore, under the situation that is aluminium, two valencys are occupied with the chelating of cyanines ring, and remaining valency causes with axial R unit and is connected.
Axial R unit
Light-sensitive compound of the present invention can randomly contain the R unit that axially is connected with the central metal or the non-metallic atom of photolytic activity cyanines member ring systems.These R unit and central atom are covalently bound.
The non-spectrochemical property that can regulate light-sensitive compound owing to axial R group occurs in a preferred embodiment of the invention.For example and be non-limiting be that axial R unit can make photosensitizers have solvability fabric durability and increase or that reduce.Formulator needs slow dissolved optical white, and it is discharged in the washing liq when cycles of washing finishes.By changing axial R unit, photobleaching character can transfer the needs that satisfy specific product preparation and application to.
Except deliquescent character, can chosen axis prevent the packing of molecules of metal cyanines ring to the R unit.Ability by restriction light-sensitive compound " accumulation " can more effectively produce singlet oxygen and be transported to destination locations.Fabric durability also can reach to the R unit by chosen axis.For containing more than a unitary molecule of axial R, formulator can be selected respectively at different character, and at one, weather resistance is at another as solvability.
Compounds effective of the present invention contains covalently bound axial R unit on central metal atom, and wherein each R selects following group respectively:
A) hydrogen;
B) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) oximido;
G) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
I) C of poly-hydroxy replacement
3-C
22Alkyl;
J) C
1-C
22Alkoxyl group, preferred C
1-C
4Alkoxyl group, more preferably methoxyl group;
K) has the collateralization alkoxyl group of following general formula
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H, OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively, preferred 0 to 6; Z can have 0 to 100 value respectively, and preferred 0 to about 10, and more preferably 0 to about 3;
L) following aryl and the substituted aryl of general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.;
M) have the alkylidene aryl of following general formula and the alkylidene aryl of replacement
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
3-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; P is 1 to about 10, preferred 1 to about 3;
N) have the aryloxy and the substituted aryloxy of following general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl ,-(CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.;
O) the alkylene oxide group arylalkyleneoxy aryl unit of alkylene oxide group aryl and replacement is the part with following general formula:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl ,-(CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; Q is 0 to about 10, preferred about 1 to about 3;
P) have the oxyalkylene aryl of following general formula and the oxyalkylene aryl of replacement:
R wherein
34And R
35Be selected from hydrogen, C respectively
1-C
6Alkyl, C
2-C
6Alkenyl, C
1-C
6Alkoxyl group, C
3-C
6The alkoxyl group of collateralization, halogen, morpholino, cyano group, nitrilo ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-N (R
36)
2With-N
+(R
36)
3X
-, R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl, (CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; Preferred hydrogen, C
1-C
6Alkyl ,-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+With their mixture, more preferably R
34Or R
35Be hydrogen, another part is C
1-C
6Wherein M is a water-soluble cationic, and X is chlorine, bromine, iodine or other water soluble anion.The example of other water soluble anion comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.; W is 1 to about 10, preferred about 1 to about 3;
Q) C
1-C
22Alkylthio, C
3-C
22Alkylthio that replaces and their mixture;
R) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be respectively C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl, R
28Be hydrogen, C
1-C
22Alkyl, C
4-C
22The alkyl of collateralization, C
3-C
22Alkenyl, C
4-C
22The alkenyl of collateralization and their mixture, A is heteroatoms nitrogen or oxygen, preferred A is an oxygen, when not having heteroatoms, v is 0, and when heteroatoms was arranged, v equaled 1, and preferred V equals 0, X is chlorine, bromine, iodine or other water soluble anion, and u is 0 to 22, and preferred u is 3 to about 10.Other water soluble anion example comprises organic anion, and as fumaric acid radical, tartrate anion, oxalate etc., inorganic anion comprises sulfate radical, bisulfate ion, phosphate radical etc.
S) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Contain C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl and their mixture;
T) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
k-(CH
2)
m(OCH
2CH
2)
nZ
A is heteroatoms nitrogen or oxygen, and preferred A is an oxygen, and when not having heteroatoms, k is 0, and when heteroatoms was arranged, k equaled 1, and Z is hydrogen, hydroxyl, C
1-C
30The aryloxy of the aryl of alkoxyl group, aryl, replacement, aryloxy, replacement, alkylidene amino ,-SO
3 -M
+,-OSO
3 -M
+,-CO
2M ,-CH
2CO
2M and their mixture, preferred hydrogen or C
1-C
30Alkoxyl group; N is 1 to 100, and preferred 0 to about 20, more preferably 2 to about 10; M is 1 to 12, preferred about 1 to about 5;
U) the following hydroxy-acid group of general formula:
R wherein
37Contain:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization and their mixture;
Ii) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization and their mixture;
The iii) C that replaces of poly-hydroxy
3-C
22Alkyl;
Iv) C
3-C
22Glycol;
V) C
1-C
22Alkoxyl group;
Vi) C
3-C
22The alkoxyl group of collateralization;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) alkylaryl of Qu Daiing, unsubstituted alkyl aryl or their mixture;
Ix) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
X) alkoxyl group of Qu Daiing, unsubstituted alkoxy aryl or their mixture;
Xi) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
Xii) alkylidene amino and their mixture;
V) following siloxy-and the siloxy-of the replacement :-OSiR of general formula
31R
32R
33, R wherein
31, R
32And R
33Be selected from C respectively
1-C
8Alkyl, C
3-C
8The alkyl of collateralization, C
2-C
8Alkenyl, C
3-C
8The alkenyl of collateralization, the alkyl of replacement, aryl, alkyl inferior ethoxyl unit, its general formula is:
-(A)
k-(CH
2)
m(OCH
2CH
2)
nZ wherein Z is hydrogen, C
1-C
30Alkyl, hydroxyl ,-CO
2H ,-SO
3 -M
+,-OSO
3 -M
+, C
1-C
6The aryloxy of the aryl of alkoxyl group, aryl, replacement, aryloxy, replacement, alkylidene amino and their mixture; A is heteroatoms nitrogen or oxygen, and M is a water-soluble cationic, and k is 0 or 1, and n from 0 to 100, and m is 0 to 12; And their mixture; With alkylidene amino unit and their mixture.
According to the present invention, preferred axially R unit contains the following part of general formula:
-Y
i-L
jWith-Y
i-Q
jWherein Y is selected from O, CR
41R
42, OSiR
41R
42, OSnR
41R
42With their connection portion of mixture; R wherein
41And R
42Be hydrogen, C
1-C
4Alkyl, halogen and their mixture; I is 0 or 1, and j is 1 to 3;
L is a ligand, is selected from:
A) C
3-C
30Linear alkyl, C
3-C
30Collateralization alkyl, C
2-C
30Linear chain thiazolinyl, C
3-C
30Collateralization alkenyl, C
6-C
20Aryl, C
7-C
20Arylalkyl, C
7-C
20Alkylaryl and their mixture;
B) alkyl inferior ethoxyl unit, general formula is:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
1-C
20Alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20The alkenyl of collateralization, C
6-C
20Aryl, C
7-C
30Arylalkyl, C
6-C
20Alkylaryl and their mixture; R
38Be selected from C
1-C
4Linear alkylene, C
3-C
4The alkylidene group of collateralization, C
3-C
6Hydroxy alkylidene and their mixture; R
39Be selected from C
2-C
20Alkyl, C
6-C
20The alkyl of collateralization, C
7-C
20Aryl, C
7-C
30Arylalkyl, C
7-C
30Alkylaryl and their mixture; X from 1 to 100; Y is 0 or 1; With
Q is the ion part, and general formula is as follows:
-R
40-P is R wherein
40Be selected from C
3-C
30Linear alkylene, C
3-C
30The alkylidene group of collateralization, C
2-C
30Linear alkylene group, C
3-C
30The alkylene group of collateralization, C
6-C
16Arylidene and their mixture; P is selected from-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M
+,-OPO
3 2-M
+,-N
+(R
36)
3X
-M is the water-soluble cationic that electroneutral enough electric charges can be provided, and X is above-mentioned water soluble anion.
Preferred axially R unit is alkyl alkylene oxide group unit, and general formula is as follows:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
3-C
20Linear alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20Collateralization alkenyl, C
6-C
10Aryl, C
7-C
20Arylalkyl, C
7-C
20Alkylaryl and their mixture; R
38Be selected from C
1-C
4Linear alkylene, C
3-C
4Collateralization alkylidene group and their mixture; R
39Be selected from C
2-C
6Alkylidene group, C
3-C
6The alkylidene group of collateralization, C
6-C
10Arylidene and their mixture; X from 1 to 50; Y is 0 or 1;
Preferred axial R contains y in the unit and equals 0, and Z is hydrogen, C
1-C
20Alkyl, C
3-C
20Collateralization alkyl, C
6-C
10Aryl and their mixture, most preferably Z is hydrogen or C
6-C
20Linear alkyl, C
10-C
20The collateralization alkyl; R
38Be C
1-C
4Linearity or C
3-C
4The alkylidene group of collateralization.
Also preferred R unit has general formula:
-Y
i-Q
jWherein Y is selected from O, CR
41R
42, OSiR
41R
42, OSnR
41R
42With their connection portion of mixture; I is 0 or 1, and j is 1 to 3; Q is the ion part, and general formula is as follows:
-R
40-P is R wherein
40Be selected from C
3-C
20Linear alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20Collateralization alkenyl, C
6-C
10Aryl and their mixture; P is selected from-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M
+,-OPO
3 2-M
+,-N
+(R
36)
3X
-R wherein
36Be selected from hydrogen, C respectively
1-C
6Alkyl ,-(CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; M is the water-soluble cationic that electroneutral enough electric charges can be provided, and X is above-mentioned water soluble anion.
The i of preferred wetting ability R equals 1; R
40Be C
3-C
20Linear alkyl, C
3-C
20The alkyl of collateralization; P is-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+M is the water-soluble cationic that electroneutral enough electric charges can be provided.
Be applicable to and have general formula:
-Y
i-L
jThe unitary example of the unitary Y of R have general formula:
-O-L
1,-Sn-L
1,-OSn-L
1Wherein i equals 1, and j equals 1.Other example has general formula
Wherein i equals 1, and j equals 3.Above-mentioned example also is applicable to the Y unit when adopting Q ion part.
Following Example explanation cyanines ring, its chelated mineral or non-metallic atom be silicon under this situation, and balance are connected the valency of the unitary central atom of axial R:
The method that the present invention relates to bleached woven fabric, organic or inorganic substrate or wipe out a blot from it; perhaps be used to protect fabric, organic or inorganic substrate not to be subjected to the method for microorganism encroach; wherein will be processed or protection be not subjected to the fabric of microorganism encroach or base material to adopt light-sensitive compound of the present invention to handle, use rayed simultaneously there being water to exist under the situation.
The present invention relates to be applicable to photo bleach compositions as laundry detergent composition.
Photo bleach compositions of the present invention contains:
A) at least about 0.001ppm, preferred about 0.01 to about 10000ppm, more preferably from about 0.1 to about 5000ppm, 10 hydridization cyanines light-sensitive compounds that arrive about 1000ppm most preferably from about, said compound contains the mixture of the hydridization cyanines ring inner complex with following general formula:
Wherein encircling A, B, C and D is aromatic nucleus, is selected from respectively to replace and unsubstituted benzene, replacement and unsubstituted naphthalene, replacement and unsubstituted anthracene, replacement and unsubstituted phenanthrene and their mixture; With
B) balance carrier and other binder component, but the preferable additives component is selected from and is not limited to buffer reagent, auxiliary agent, sequestrant, filling salt, stain remover, dispersion agent, enzyme, enzyme promotor, spices, thickening material, clay, SYNTHETIC OPTICAL WHITNER, solvent and their mixture.
Preferred photo bleach compositions contains the light-sensitive compound that further contains the photolytic activity metal.The photo bleach compositions of the present invention that contains the metal cyanines contains:
A) at least about 0.001ppm, preferred about 0.01 to 10000ppm, more preferably from about 0.1 arrive about 5000ppm, most preferably from about 10 to the hybridized metal cyanines photosensitive mixtures of 1000ppm, this mixture contains two kinds or more of, preferred about 3 to about 100 kinds, more preferably from about 10 below about 100 kinds have the hybrid compounds of general formula:
Wherein every kind of mixture metal cyanines contain:
A) photolytic activity metal or nonmetal M, wherein said photolytic activity metal or nonmetal M are selected from silicon, germanium, tin, lead, aluminium, platinum, palladium, phosphorus and their mixture, and condition is that said metal or nonmetallic valency are 3 or 4;
B) aromatic nucleus A, B, C and D, wherein each ring be selected from replacement respectively or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, anthracene, phenanthrene and their mixture; With
C) the axial R unit of adjusting solubleness and weather resistance; The value of t is 1 or 2;
Condition is that the Q band maximum absorption wavelength scope of every kind of photosensitizers of said mixture is 600 nanometers or bigger, and said metal cyanines as described herein;
B) at least about 0.1%, preferred about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to the detergent surfactant of about 20% weight, and said detergent surfactant is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture; With
C) balance carrier and other binder component, said binder component is selected from buffer reagent, auxiliary agent, sequestrant, filling salt, stain remover, dispersion agent, enzyme, enzyme promotor, spices, thickening material, clay, SYNTHETIC OPTICAL WHITNER, solvent and their mixture.
The present invention relates to a kind of methods for photobleaching fabrics, comprise the fabric of needs cleanings is contacted with the moisture cleaning solution that contains at least about the photosensitive composition of the present invention of 0.001ppm that then the surface of the fabric that will handle is exposed to the minimum wavelength scope at about 300 light sources that arrive about 1200 nanometers.
Usually light source is a sunlight, and by fabric is suspended on the ventilation fabric is exposed to sunlight after employing contains the solution-treated of photosensitizers of the present invention.Light source also can provide in the process that adopts the liquid lime chloride washing.For example, can use to comprise having suitable wavelength, preferred about 300 arrive the washing machine of the light source of about 1200 nanometers.
The intensity of irradiation can change in wide region, and as for the bleaching efficiency of specific compound of the present invention, this depends on the concentration of active substance and the situation of light source.Other parameter that can change is exposure duration, and promptly for same result, lower optical density(OD) must expose the longer time than higher optical density(OD).Usually, according to the field of being adopted, exposure duration can be from the several minutes to the several hrs.
If this technology is carried out (for example sterilization of fabric) in water medium, adopt rayed directly in treatment media, to carry out by the source of artificial light that is placed in the medium or medium is outer, perhaps follow under the situation of humidity, goods again by the source of artificial light irradiation, perhaps are exposed to sunlight.Obtain good sterilization effect and can adopt the very active substance of lower concentration, for example 0.001ppm.According to use field and the photosensitive derivative of hydridization cyanines that adopted, concentration is 0.005 and 2000, preferred 0.01 and 1000ppm between.
The invention still further relates to a kind of method of smooth disinfecting surface, comprise that the clean aqueous solution of 0.001ppm photosensitive composition of the present invention contacts with containing at least with needing clean Surface, the surface that to handle is exposed to and has the suitable wavelength scope again, preferred about 300 light sources to about 1200 nanometers.
Method of the present invention also can be finished in solvent-based carrier or in low aqueous solution.Based on purpose of the present invention, said low water-based is meant water is joined in the carrier system, changes the character of carrier, not merely is in order to make the matrix solubilising.For example, preferably can retain the solvent that dissolved oxygen also can form miscible system with water.The indefiniteness example of these solvents is butoxy propoxy-propyl alcohol (BPP), methoxy propoxy propanol (MPP), oxyethyl group propoxy-propyl alcohol (EPP) and propoxy-propoxy-propyl alcohol (PPP).The embodiment of the present invention that contain these non-classical aqueous compositions are very effective when this SYNTHETIC OPTICAL WHITNER must be used to contain the fabric of the medium that rejects water and moisture or surface.
The sterilization of the fabric of synthetic or natural origin can be used as important purposes and mentions.Can adopt method sterilization of the present invention in family or at the industrial thing that will wash.For this purpose, the thing that wash can adopt the hydridization cyanines aqueous solution of the present invention to handle with rayed simultaneously in the above-mentioned mode of mentioning.Advantageously the hydridization cyanines can with every liter 0.01 to about 2000, preferred 0.1 to 1000, more preferably 0.1 to 500 milligram amount is present in the treatment media.Advantageously sterilization can be carried out with washing step.For this reason, adopt the washing medium that contains conventional washing composition material, one or several hydridization cyanines of the present invention, inorganic salt as required and/or other additive to handle the thing that will wash.Washing process can manually carry out, and for example in basin, perhaps carries out in washing machine.Be exposed in the light and can in washing process, adopt suitable light source to carry out, perhaps also the moist material of washing then for example can be exposed to suitable source of artificial light or be exposed to sunlight simply in drying process, for example linear dry.
Superficial bleaching can be undertaken by for example the aqueous solution of hydridization cyanines light-sensitive compound of the present invention being used for suitable surface, and this solution preferably contains 0.001 active substance to about 10% weight of having an appointment.This solution also can contain other conventional additives in addition, for example wetting agent, dispersion agent or emulsifying agent, washing composition material and inorganic salt as required.After using this solution, simply this surface is exposed to sunlight, perhaps it can adopt the artificial light irradiation in addition as required.Suggestion keeps surface moisture in light irradiation process.
Hydridization photosensitizers of the present invention can be modified, to have the surperficial affinity of wide region.Make molecule " durable " or " not durable " by chosen axis to the R unit.The present invention's said " weather resistance " is meant the character that makes that optical white successfully contacts with specific purpose surface.For example, in specification sheets of the present invention, put down in writing, can chosen axis to radicals R, make the goods of photobleaching mixture and synthetic textiles, durable surface (as ceramic tile) or common any fabric, production or need the position of bleaching compatible.
For example, R unit and desired substance (as fabric) or corresponding with the textural property of purpose matrix (as stain).The unitary ability of R of selecting is depended in the selection of modifying R unit character, thereby makes optical physics unaffected with the process of finishing hydridization cyanines ring is irrelevant.
Other advantage of photosensitizers of the present invention and photobleaching system is that they are more safer to fabric and color than conventional whiteners (as hypochlorite).Without being limited by theory, can believe that the security that improves fabric and color is because the tinting material that uses has suppressed singlet oxygen when producing band look product.
" not durable " molecule is that utilization is needed in the time must being deposited in the liquid at light-sensitive compound rather than be attracted to concrete surface, as the sterilization of water.
Low key tone optical white and light sterilizing agent are preferred embodiments of the present invention.Said " low key tone " herein with whole specification sheets in be meant optical white Q band λ max greater than about 700 nanometers, and therefore people's eyes are had only slight sensation.Q band maximum wavelength of the present invention other material of (as 660～700 nanometers) in " as seen " scope is a light disinfecting substance the most suitable when the sensation to coloring matter is not the factor of overslaugh use.
Hydridization cyanines of the present invention have multiple Q band (each hydridization cyanines ring has independent Q band).This is with to have the common photosensitive solution with the corresponding Q of color band different.By selecting monomer, Q band peak can cross over that spectrum band launches relatively equably or this peak may be superimposed.Final optical property is judged by formulator.
Based on the generation of the molecule of singlet oxygen, can expect effective photobleaching, this theory has been passed through a large amount of research, and can be understood by the technician in photobleaching field.Because the singlet oxygen material life-span is short, be major advantage so have photosensitive molecular near will be by the stain of " attack ".
Molecule of the present invention can be at any desired position owing to the ability of formulator control " weather resistance ".The another kind of layering that prevents photosensitive molecular that has owing to the unitary axial configuration of R and the ability of accumulation provide effective individual layer.For example, the present invention is used for needing hydridization cyanines light-sensitive compound to have affinity to fabric face from the embodiment that fabric wipes out a blot, and the photobleaching compound is near the position that need work.These requirements all can be satisfied by changing a kind of or several R unit.
Known phthalocyanine and naphthalene cyanines ring can the absorb light quantum and are formed electron excitation material (singlet and triplet state), and these materials can be produced ' oxygen species that is excited ' by oxygen quenching.Particularly preferred ' oxygen species that is excited ' is singlet oxygen, and it is very easy to suppress photosensitizers by molecular oxygen, forms as the triplet state of phthalocyanine.Therefore, the purpose of hydridization cyanines photobleaching formulator is to produce the compound that helps forming triplet state.
When using up the irradiation photosensitizers, the single times of energy state that is produced has experienced various processes, i.e. the secondary rays of light (fluorescence).Most important method about the photobleaching that adopts singlet oxygen is intersystem crossing (ISC).This is the mechanism that singlet is converted to triplet state.Usually, the efficient of this method is discussed with this term of quantum yield, promptly produces the absorbed photon number of required triplet excited state.The present invention provides the enhanced photobleaching by improving intersystem crossing from the efficient that singlet state becomes triplet state.Molecule of the present invention can be changed by formulator, to improve the quantum yield that forms triplet state thus.Be that formulator can change phthalocyanine ring monomer type and cyclosiloxane monomer substituting group by for example " heavy atoms effect " known in the art unexpectedly, to improve the productive rate of triplet state quantum.Selection to the part of its " heavy atoms effect " can be irrelevant with other factors, for example needn't consider the solubleness factor.This is because irrelevant to R group and the change that hydridization cyanines member ring systems is done at the solubleness chosen axis.
Laundry composition of the present invention randomly contains detergent surfactant, for example negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics, but formulator is not limited to these examples or their combination.The amount of tensio-active agent be composition about 0% to about 95%, preferred about 5% to about 30% weight.
Cleaning compositions of the present invention randomly contains detergent surfactant, for example negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics, but formulator is not limited to these examples or their combination.The amount of tensio-active agent be composition about 0% to about 50%, preferred about 5% to about 30% weight.
Laundry composition of the present invention randomly contains auxiliary agent, for example silicate, carbonate and zeolite, but the user is not limited to these examples or their combination.The amount of auxiliary agent be composition about 0% to about 50%, preferred about 5% to about 30% weight.
Cleaning compositions of the present invention randomly contains auxiliary agent, for example silicate, carbonate and zeolite, but the user is not limited to these examples or their combination.The amount of auxiliary agent be composition about 0% to about 50%, preferred about 5% to about 30% weight.
Hard surface cleaner of the present invention randomly contains auxiliary agent, for example silicate, carbonate and zeolite, but the user is not limited to these examples or their combination.The amount of auxiliary agent be composition about 0% to about 50%, preferred about 5% to about 30% weight.
Hard surface cleaner of the present invention randomly contains abrasive, measure into composition about 0.5% to about 85%, preferred about 10% to about 85% weight.Suitable abrasive is silicate, carbonate, perlite, clay and ceramic powder clay, and still, the user is not limited to these examples or their combination.
The invention still further relates to a kind of method, wherein one or several hydridization cyanine compounds exist under the situation of oxygen with therein or the medium that carries out said reaction on it contact, perhaps join in this medium, and use rayed.
If this method is to carry out (for example to textile disinfecting) in hydration medium, can directly be undertaken by the artificial light that is placed in the medium or outside the medium in treatment media with rayed, perhaps then matrix adopts the artificial light irradiation again or is exposed to sunlight under dampness.The sterilization effect that The compounds of this invention is good can adopt the very active substance of lower concentration, and for example 0.001ppm obtains.According to the field of using and the phthalocyanine or the naphthalene cyanines derivative that are adopted, concentration is 0.005 to 100, preferred 0.01 to 50ppm.
Can also add in the methods of the invention and can improve active material, ionogen particularly, inorganic salt for example are as sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, sodium acetate, ammonium acetate, alkali metal phosphate and alkali metal tripolyphosphates, particularly sodium-chlor and sodium sulfate.These salt can join according to the present invention in the reagent, perhaps can directly add in using method, so that they exist with the concentration that is preferably 0.1 to 10% weight in using solution.
Aqueous solution is meant it is the solution of water basically, and still, formulator can comprise additive materials and tensio-active agent, to help removing " processing " microorganism in the cleaning process of washing or back.
Tensio-active agent-instant cleaning compositions contains the tensio-active agent of 0.1% to 60% weight of having an appointment, and tensio-active agent is selected from negatively charged ion, nonionic, amphoteric, zwitterionic tensio-active agent.For liquid system, the tensio-active agent preferred content is about 0.1% to 20% weight of composition.For solid (as particle) and viscosity semisolid (as gel, mashed prod etc.) system, the content of tensio-active agent is preferably about 1.5% to 30% weight of composition.
The spendable indefiniteness surfactant concentrations of the present invention is generally about 1% to 55% weight, comprises conventional C
11-C
18Alkylbenzene sulfonate (" LAS ") and uncle collateralization and random C
10-C
20Alkyl-sulphate (" AS "), C
10-C
18Secondary (2,3) alkyl-sulphate, general formula is CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3, wherein x and (y+1) be to be at least about 7 integer preferably is at least about 9, and M is a water-soluble cationic, sodium ion particularly, undersaturated vitriol for example is oleyl sulfate, C
10-C
18Alkyl alkoxy sulfate (" AE
xS ", the ethoxy sulfate of E01-7 particularly), C
10-C
18Alkyl alkoxy carboxylate salt (the particularly ethoxy carboxylate of E01-5), C
10-C
18Glyceryl ether, C
10-C
18The poly-glycosides of alkylpolyglycosides and their corresponding sulphatings, and C
12-C
18α-sulfonated fatty acid ester.If desired, conventional nonionic and amphoterics, for example C
12-C
18Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C
6-C
12Alkylphenol alcoxylates (particularly ethoxylate and blended oxyethyl group/propoxy-), C
12-C
18Trimethyl-glycine and sultaine (" sultains "), C
10-C
18Amine oxides etc. also can be included in the above-mentioned composition.Can also use C
10-C
18N-alkyl polyhydroxy fatty acid amide.General example comprises C
12-C
18The N-methyl glucose amide.Referring to WO9206154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low foamy.Also can adopt C
10-C
20Conventional soap.High if desired foamy can adopt side chain C
10-C
16Soap.The mixture of negatively charged ion and nonionogenic tenside is particularly preferred.Other tensio-active agent commonly used is also put down in writing in the present invention and is listed in the standard article.
Anion surfactant can be described as be at the water-soluble salt, particularly an alkali metal salt that has to contain the 8 organosulfur acid-respons products that are selected from sulfonic acid and sulfate group to alkyl and of about 22 carbon atoms of having an appointment in its molecular structure widely.(the moieties that in said alkyl, comprises senior acyl group.) important example of anion synthetic detergent that can be used as the surface active agent composition of composition of the present invention is sodium alkyl sulfate or potassium, particularly those are by the higher alcohols (C of sulfation by the glyceryl ester preparation of reduction tallow or Oleum Cocois
8-C
18Carbon atom) prepared; Sodium alkyl benzene sulfonate or potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, (alkyl can be the aliphatic chain of straight chain or collateralization); Alkyl glycerol base ether sulfonic acid sodium, particularly those are by the ether of the higher alcohols of tallow and Oleum Cocois generation; Coco-nut oil fatty acid monoglyceryl ester sodium sulfate and sodium sulfonate; One mole of high fatty alcohol (as tallow alcohol or coconut alcohol) and about 1 sodium salt or sylvite to the sulfuric ester of the reaction product of about 10 moles of ethylene oxide; Per molecule have about 1 to the oxyethane of about 10 units and wherein alkyl contain the sodium salt or the sylvite of the alkylphenol oxyethane ether sulfuric ester of 8 to 12 carbon atoms; The reaction product of the lipid acid that produces from Oleum Cocois; Lipid acid wherein for example, is the sodium salt or the sylvite of the tatty acid acid amides of the methyl tauryl amine that produced by Oleum Cocois, and β-acetoxyl or β-acetylaminohydroxyphenylarsonic acid alkyl sulfonic acid sodium or potassium, and wherein alkyl contains 8 to 22 carbon atoms.
In addition, formulator can only adopt secondary alkyl sulfate, perhaps it is used in combination with other surfactant materials, below discriminated union difference between Sulfated tensio-active agent and other the conventional alkyl sulfate surfactant is described.The non-limiting example of this class component is as follows.
Conventional primary alkyl sulphates (LAS) as top said, has general formula R OSO
3 -M
+, wherein R generally is linear C
8-C
22Alkyl, M are water-soluble cationics, for example LAS sodium.The chain primary alkyl sulphates tensio-active agent (being collateralization chain " PAS ") that has the collateralization of 8 to 20 carbon atoms also is known; For example referring to EP439316, Smith etc., on January 21st, 1991.
Conventional secondary alkyl sulfate surfactant is the material that alkyl " main chain " random distribution along molecule the sulfuric ester part.This class material can be with following structrual description:
CH
3(CH
2)
n(CHOSO
3 -M
+) (CH
2)
mCH
3Wherein m and n are 2 or greater than 2 integer, and the sum of m+n generally is about 9 to 17, and M is a water-soluble cationic.
Above-mentioned secondary alkyl sulfate prepares by add sulfuric acid in alkene.Adopt that α alkene and vitriolic typical case is synthetic to be disclosed in US3234258, Morris, on February 8th, 1966 or at US5075041, Lutz is in 24 days December in 1991.Can produce the second month in a season the following product of synthetic generation that carries out in the solvent of (2,3) alkyl-sulphate after cooling, this product is at removal unreacted matters, random sulfation material, the not Sulfated by product of purifying, as C
10During with higher alcohols, secondary sulfonated alkene etc., the pure mixture (can have some sodium sulfate) of 2-more than 90% and 3-sulfation material normally, and be solid white, inviscid, that obvious crystalline form is arranged.Also can exist some 2,3-dithionate, but contain the mixture that is not more than (2,3) alkyl one vitriol second month in a season of 5% usually.This class material can be with " DAN ", is provided by Shell Oil Company as the trade(brand)name of " DAN 200 ".
SYNTHETIC OPTICAL WHITNER and bleach activator-detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or several bleach activators.When containing SYNTHETIC OPTICAL WHITNER, its amount normally in particular for the detergent composition of fabric washing about 1% to about 30%, more preferably from about 5% to 20%.If contain bleach activator, its amount is generally and contains bleaching composition about 0.1% to 60% that SYNTHETIC OPTICAL WHITNER adds bleach activator, more generally is about 0.5% to 40%.
The SYNTHETIC OPTICAL WHITNER that the present invention adopts can be any can be used for the present known of clean fabric, hard-surface cleaning or other purposes or will known detergent composition in SYNTHETIC OPTICAL WHITNER.They comprise the oxygen bleaching agent except that hypohalite (as clorox) SYNTHETIC OPTICAL WHITNER.The present invention can adopt perborate (as water or four water sodium salts) and percarbonate bleach.
The indefiniteness SYNTHETIC OPTICAL WHITNER of other kind comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprises Magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoic acid magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in US4483781, on November 20th, 1984, Hartman; US740446, on June 3rd, 1985, Burns; EP0133354, on February 20th, 1985, Banks etc.; US4412934, November 1 nineteen eighty-three is among the Chung etc.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid, as at US4634551, and on January 6th, 1987, record among the Burns etc.
Also can adopt peroxygen bleach.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate and equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can adopt persulphate SYNTHETIC OPTICAL WHITNER (as the OXONE of the industrial production of DuPont).
Preferred percarbonate bleach contains dried particles, and its mean particle size arrives in about 1000 microns scope at about 500 microns, and the said particle that is not more than about 10% weight is less than about 200 microns, and the said particle that is not more than about 10% weight is greater than about 1250 microns.Randomly be that this percarbonate can be coated by silicate, borate or water soluble surfactant active.Percarbonate can be provided by each industrial structure, for example FMC, Solvay and Tokai Denka.
Can also adopt the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach activator, and it can be so that prepare peroxy acid (promptly in washing process) corresponding to bleach activator on the spot in the aqueous solution.The non-limiting example of each of promoting agent is disclosed in Mao etc. and obtains among the US4915854 and US4412934 of power in April 10 nineteen ninety.Generally be nonanoyl oxygen benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) promoting agent, also can adopt their mixture.Referring to other type SYNTHETIC OPTICAL WHITNER and the promoting agent among the US4634551.
The general formula of acid amides deutero-bleach activator very preferably is:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L is R wherein
1Be the alkyl that contains 6 to 12 carbon atoms of having an appointment, R
2Be the alkylidene group that contains 1 to 6 carbon atom of having an appointment, R
5Be hydrogen or alkyl, aryl or the alkaryl that contains 1 to 10 carbon atom, L is any suitable leavings group.Leavings group be since cross the hydrolysis negatively charged ion to bleach activator carry out nucleation the result and from bleach activator by any group of metathetical.Preferred leavings group is the Phenylsulfonic acid root.
Preferred embodiment with bleach activator of above-mentioned general formula comprises (6-decoylamide-caproyl) oxygen benzene sulfonate, (6-pelargonamide caproyl) oxygen benzene sulfonate, (6-decanoyl-caproyl) oxygen benzene sulfonate and their mixture, and they are documented at this in conjunction with among the US4634551 as a reference.
Other kind of bleach activator is included in the promoting agent of disclosed benzo oxazinyl in the US4966723 of bulletin on October 30 nineteen ninety such as Hodge, this patent at this in conjunction with as a reference.Benzo oxazinyl promoting agent very preferably is:
Also have another kind of preferred bleach activator to comprise the acyl lactam promoting agent, particularly have the acyl caprolactam and the acyl group Valerolactim of following general formula:
R wherein
6Be hydrogen or contain 1 to alkyl, aryl, alkoxy aryl or the alkaryl of about 12 carbon atoms.Lactan promoting agent very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.Also can obtain the US4545784 of power on October 8th, 1985 referring to Sanderson, in conjunction with as a reference, it discloses the acyl caprolactam that is absorbed in the Sodium peroxoborate, comprises benzoyl caprolactam at this for it.
In fact, and also right and wrong are determinate, the compositions and methods of the invention can be adjusted so that the active bleaching catalyst of 0.1ppm at least to be arranged in washing liquid, and preferably provide about 0.1ppm to about 700ppm in washing liquid, and more preferably from about 1ppm arrives the catalyst substance of about 500ppm.
SYNTHETIC OPTICAL WHITNER except oxygen bleaching reagent also is known in the art and also can be used for the present invention.One class especially effectively non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonated Phthalocyanine Zinc and/or aluminium.Obtain the US4033718 of power on July 5th, 1977 referring to Holcombe etc.If adopt, detergent composition generally contains 0.025% this class SYNTHETIC OPTICAL WHITNER, particularly sulfonic acid Phthalocyanine Zinc to about 1.25% weight of having an appointment.
Buffer reagent-buffer reagent can be included in the preparation of various uses.A kind of purposes is to adjust clean surface pH, to optimize the effect of this hard-surface cleaning compositions to the dirt and the stain of particular type.Can add buffer reagent comes the stabilization additives component to prolong storage life or in order to keep the consistency between the various components.Hard surface cleaner of the present invention can randomly contain buffer reagent adjusts pH about 7 to about 13, and preferred about 8 to about 13, and more preferably from about 10 in about 11 scope.The indefiniteness example of suitable reducing is salt of wormwood, yellow soda ash and sodium bicarbonate, and still, formulator is not limited to these examples or their combination.
Additive materials
Composition of the present invention can randomly contain one or several other detergent additives materials or other material that helps or improve cleaning effect, processing requirements clean Surface or improve the aesthetic measure (as spices, dyestuff, pigment etc.) of composition.The following describes the example of this class additive materials, but be not to get rid of or the qualification of scope.
Sequestrant-detergent composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, the fragrant chelating agent of polyfunctional group replacement and their mixture, and they all describe in the back.Although do not want to be limited by theory, can think that the effect part of these materials is to remove the unexpected ability of iron and mn ion because they have by forming the soluble chelating thing from washing soln.
The aminocarboxylate of useful as selective sequestrant comprises ethylene diaminetetraacetic acid salt, N-hydroxyethyl ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylene diamine four propionic salts, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their ammonium salt of basic metal, ammonium and replacement and their mixture.
When allowing the total phosphorus of low levels at least in detergent composition, amino phosphonates do also is applicable in composition of the present invention as sequestrant, and comprises ethylene diamine four (methylene phosphonic acid salt), as DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.
The fragrant chelating agent that polyfunctional group replaces also is applicable to composition of the present invention.Referring to US3812044, on May 21st, 1974, Connor.The preferred compound of this class acid form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
The preferred biodegradable cheating agent that the present invention adopts is ethylene diamine two succinates (" EDDS "), and particularly [S, S] isomer as US4704233, on November 3rd, 1987, is put down in writing among Hartman and the Perkins.
If use, the amount of these sequestrants generally is that about 0.1% of detergent composition of the present invention arrives about 10% weight.If use, more preferably this sequestrant is that about 0.1% of said composition arrives about 3.0% weight.
The indifferent salt (filling salt) of indifferent salt-the be used for present composition can be the mixture of any water miscible inorganic salt or organic salt or this class salt, and they can not make the tensio-active agent instability.Based on purpose of the present invention, " water-soluble " is meant that the solubleness in water is at least 1 gram in the water of 20 ℃ of per 100 grams.The example of suitable salt comprises vitriol, muriate, borate, bromide, fluorochemical, phosphoric acid salt, carbonate, supercarbonate, Citrate trianion, acetate, lactic acid salt of various basic metal and/or alkaline-earth metal etc.
The specific examples of suitable salt comprises sodium sulfate, sodium-chlor, Repone K, yellow soda ash, vitriolate of tartar, lithium chloride, Lithium Sulphate, Tripotassium phosphate, Sodium Tetraborate, Potassium Bromide, Potassium monofluoride, sodium bicarbonate, sal epsom, magnesium chloride, Trisodium Citrate, sodium-acetate, magnesium lactate, Sodium Fluoride.Preferred salt is to be preferably alkali metal sulfates and muriatic inorganic salt.Particularly preferred salt is because its low price but sodium sulfate and sodium-chlor.The amount of this salt in composition is 0% to 40%, preferred 10% to 20%.
The main ingredient of the semi-solid hard-surface cleaning compositions of abrasive material-most solids or thickness is the abrasive material material that adds in order to be beneficial to washing operation.Abrasive material clean sanitising agent provide a kind of mode easily and effectively sterilize porcelain and watt surface, particularly basin, shower and lavatory basin.Abrasive material particles material in said composition plays to wipe and loosen and adheres to dirt on the crust, and further makes the crust dirt and be present in tensio-active agent in the cleaning compositions and/or the tight contact between the SYNTHETIC OPTICAL WHITNER.
Abrasive cleaners generally contains water-insoluble harder particulate matter as the abrasive material agent.This most frequently used class abrasive material agent is finely divided silica sand, and its granularity is about 1 to 300 micron, and proportion is about 2.1 or higher.At this class material very effectively when wanting processed surface to wipe dirt and stain, this class abrasive material material have be difficult to wash off from bathtub, shower or bathtub surface may.
Under the situation of or highly water-soluble abrasive material material (as yellow soda ash) medium, can adopt inferior amido dithionate as single abrasive material or a part of abrasive material of being added at needs.
The abrasive composition that has been found that the required type of this class can be used in combination the pearlstone abrasive material of grain type with tensio-active agent, packing material and other above-mentioned optional cleaning substance component.Be applicable to that abrasive material material of the present invention is included in US4051056, Hartman, in 27 days September in 1977 and its at this in conjunction with as a reference.
Spices-spices is in particular for the important component of liquid composition.The common consumption of spices is 0% to 5%.At US4246129, Kacher discloses some fragrance materials on January 20th, 1981 (in this combination as a reference), and they play the adjection of the solubleness that reduces anionic sulphonate and sulfate surfactant.
The content of dyestuff-dyestuff is about 0.5% to 12%, and preferred 1.5% to 5%.Spices be formed and do not contained to solid and thickness semisolid can by 1.5% dyestuff.The example of suitable dyestuff is Alizarine Light Blue B (C.I.63010), Carta BlueVP (C.I.24401), Acid Green 2G (C.I.42085), Astrogen GreenD (C.I.42040), Supranol Cyanine 7B (C.I.42675), Maxilon Blue3RL (C.I.Basic Blue 80), Drimarine Blue Z-RL (C.I.Reactive Blue18), Alizarine Light Blue H-RL (C.I.Acid Blue 182), FD﹠amp; C BlueNo.1 and FD﹠amp; C Green No.3.(referring to Kitko, US4248827, on February 3rd, 1981 and US4200606, all are incorporated herein by reference on April 29th, 1980) C.I. is meant Color Index.
Binder component-randomly as preferred version, be used for conventional additives component of the present invention and can be selected from general component, as the content of enzyme (compatible), particularly proteolytic enzyme, lipase, cellulase, coloured bespeckle, profoamer, froth suppressor, anti-dark agent and/or anticorrosive agent, soil-suspending agent, sterilant, alkaline matter, hydrotropic agent, antioxidant, enzyme stabilizers, solvent, clay soil sequestrant with other binder component be generally the present composition about 0.1% to about 10% weight.More preferably be if adopt, the content of sequestrant is this based composition removal/anti-redeposition agent, polymeric dispersant, dye transfer inhibitor, comprise polyamine N-oxide, for example about 0.1% to about 3.0% of the multipolymer of Polyvinylpyrolidone (PVP) and N-vinyl imidazole and N-vinyl pyrrolidone etc.
Embodiment 1
Prepare 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines dichloride
Toward 1,3-diimine isoindoline (0.333 gram, 2.3 mmoles), 1 adds silicon tetrachloride (2.21 grams, 12.9 mmoles) under argon gas in the mixture of 3-diimine benzene [f] isoindoline (1.35 grams, 6.9 mmoles) and anhydrous quinoline (15 milliliters).This mixture is placed in the oil bath that is preheating to 60 ℃, under this temperature, kept 30 minutes, in 30 minutes, slowly be heated to backflow, keep refluxing 30 minutes, again at 1 hour internal cooling.Add methyl alcohol (10 milliliters), again reaction soln was placed 24 hours in room temperature.Filter and collect the green solid that generates, with 10 ml methanol washed twice, 120 ℃ of dryings, need not further purifies uses under vacuum.
Embodiment 2
Prepare 1: 2 silicon (IV) phthalocyanine/naphthalene cyanines dichloride
Above-mentioned steps is applicable to said amount and adopts following 1: 2 silicon (IV) of reagent preparation phthalocyanine/naphthalene cyanines dichloride: 1,3-diimine isoindoline (0.333 gram, 2.3 mmole), 1,3-diimine benzene [f] isoindoline (0.944 gram, 4.6 mmole) and silicon tetrachloride (1.65 gram, 9.6 mmoles).
Embodiment 3
Prepare 1: 1 silicon (IV) phthalocyanine/naphthalene cyanines dichloride
Above-mentioned steps is applicable to said amount and adopts following 1: 1 silicon (IV) of reagent preparation phthalocyanine/naphthalene cyanines dichloride; 1,3-diimine isoindoline (0.333 gram, 2.3 mmoles), 1,3-diimine benzene [f] isoindoline (0.449 gram, 2.3 mmoles) and silicon tetrachloride (1.11 grams, 6.44 mmoles).
Embodiment 4
Prepare 1: 1 two lithium eight chlorine phthalocyanine/naphthalene cyanines
Toward 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles) and 4 adds lithium grain (1.17 grams, 168.6 mmoles) in the solution of 5-two chloro-phthalonitriles (5.54 grams, 28.1 mmoles) in the anhydrous 1-butanols (200 milliliters) that refluxes under argon gas is covered.This solution was refluxed 6 hours, uses anhydrous methanol (500 milliliters) dilution again, and remain on 0 ℃ 18 hours.Filter and collect the green solid that generates, dry under 80 ℃ vacuum, need not further purifies uses.
Embodiment 5
Prepare 1: 3 two lithium dichloro phthalocyanine/naphthalene cyanines
Above-mentioned steps is applicable to said amount and adopts following 1: 3 two lithium dichloro phthalocyanine/naphthalene cyanines of reagent preparation; 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles), 4,5-dichloro phthalonitrile (1.85 grams, 9.67 mmoles) and lithium grain (0.79 gram, 113.3 mmoles).
Embodiment 6
Prepare 1: 1 two lithium eight butoxy phthalocyanine/naphthalene cyanines
Above-mentioned steps is applicable to said amount and adopts following 1: 1 two lithium eight butoxy of reagent preparation phthalocyanine/naphthalene cyanines; 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles), 3,6-dibutoxy phthalonitrile (7.65 grams, 28.1 mmoles) and lithium grain (1.17 grams, 168.6 mmoles).
Embodiment 7
Prepare 1: 3 two lithium eight butoxy phthalocyanine/naphthalene cyanines
Above-mentioned steps is applicable to said amount and adopts following 1: 3 two lithium eight butoxy of reagent preparation phthalocyanine/naphthalene cyanines; 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles), 3,6-dibutoxy phthalonitrile (2.55 grams, 9.76 mmoles) and lithium grain (0.79 gram, 113.3 mmoles).
Embodiment 8
Prepare 1: 1 two lithium four butoxy phthalocyanine/naphthalene cyanines
Above-mentioned steps is applicable to said amount and adopts following 1: 1 two lithium four butoxy of reagent preparation phthalocyanine/naphthalene cyanines; 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles), 3,6-dibutoxy phthalonitrile (5.62 grams, 28.1 mmoles) and lithium grain (1.17 grams, 168.6 mmoles).
Embodiment 9
Prepare 1: 3 two lithium four butoxy phthalocyanine/naphthalene cyanines
Above-mentioned steps is applicable to said amount and adopts following 1: 3 two lithium four butoxy of reagent preparation phthalocyanine/naphthalene cyanines; 2,3-dicyano naphthalene (5.0 grams, 28.1 mmoles), 3,6-dibutoxy phthalonitrile (1.87 grams, 9.76 mmoles) and lithium grain (0.79 gram, 113.3 mmoles).
Embodiment 10
With two lithium phthalocyanine preparation phthalocyanines
Step below adopting is with two lithium phthalocyanine preparation phthalocyanines.In the solution of DMF (200 milliliters), add 1N HCl (10 milliliters) toward two lithium phthalocyanines (2 gram).This solution was at room temperature stirred 1 hour.In about 30 minutes, in this solution, add distilled water (200 milliliters).Filter the solid phthalocyanine of collecting precipitation, in a vacuum 100 ℃ of dryings, and the use of can further not purifying.
Embodiment 11
Prepare 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines-two-[poly-(ethylene glycol 350) methyl ether]
With 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines dichloride (1.0 gram, 1.31 anhydrous poly-(ethylene glycol 350) methyl ether (36.78 grams mmole),, 105.1 mixture mmole) joins in the dry DMF (150 milliliters), and with this solution with being heated to stream in 3 hours, under argon gas, refluxed 48 hours afterwards.Then with this solution cool to room temperature, go down to desolventize in vacuum, the product of generation need not further to purify to use.
This step also is applicable to 1: 3 silicon (IV) phthalocyanine-naphthalene cyanines-two (Neodol 23-6.5) of preparation and 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines-two-[glycerine-two-(Diethylene Glycol methyl ether)].
Embodiment 12
Prepare 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines-two (trolamine Dimethylsulfate guat)
With 1: 3 silicon (IV) phthalocyanine/naphthalene cyanines dichloride (0.5 gram, 0.655 mmole) and anhydrous trolamine (10 the gram, 67.04 mixture mmole) joins in the dry DMF (150 milliliters), and with being heated to backflow in 1 hour, refluxed again other 2 hours. remove solvent in a vacuum, the oil that generates is dissolved among the DMF (25 milliliters), and joins lentamente in about 800 ml waters and carry out crystallization.The green solid that filter to collect generates, and under vacuum 80 ℃ of dryings.Then at room temperature product is suspended in methyl-sulfate (0.24 gram, 1.965 mmoles) in the solution of anhydrous Dui diox (100 milliliters) 18 hours.Filter and collect the green solid that generates, drying also need not the use of further purifying.
Cleaning compositions provided by the invention can be particle, liquid, piece etc., and generally being configured to pH is 9 to 11, still, is being under the anhydrous situation or under the situation of low water composition, and the scope of pH can be outside this scope.Various carriers, for example sodium sulfate, water, water-ethanol, BPP, MPP, EPP, PPP, yellow soda ash etc. can be used to dispose final product.The product that it is 350～950g/l by jet drying or coalescent preparation density that particle can adopt known technology.Piece can adopt conventional extrusion technique preparation.Photobleaching-sequestrant can prepare if necessary in advance.Said composition also can contain general spices, sterilant, hydrotropic agent etc.Be anhydrous or the situation of low water composition under, this cleaning compositions can be used for goods, it normally is used for fabric or crust with composition of the present invention.Be the indefiniteness embodiment of composition of the present invention below:
Embodiment 13～16
Weight %
| Component | ????13 | ????14 | ????15 | ????16 |
| LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium | ????15 | ????30 | ????20 | ????25 |
| NEODOL | ????1 | ????1 | ????1 | ????1 |
| The alkyl-dimethyl ammonium chloride | ????0.5 | ????1 | ????0.5 | ????0.7 |
| Tripoly phosphate sodium STPP | ????15 | ????35 | ????22 | ????28 |
| Yellow soda ash | ????10 | ????10 | ????15 | ????15 |
| SOKALAN | ????2 | ????2 | ????2 | ????2 |
| Carboxymethyl cellulose | ????1 | ????1 | ????1 | ????1 |
| Tinopal?CBS-X | ????0.1 | ????0.1 | ????0.1 | ????0.1 |
| Stain remover 1 | ????0.2 | ????0.2 | ????0.3 | ????0.3 |
| Savinase?6.0T | ????0.3 | ????0.6 | ????0.5 | ????0.6 |
| Ban?300T | ????0.2 | ????0.5 | ????0.5 | ????0.6 |
| Lipolase?100T | ????0.1 | ????0.2 | ????0.2 | ????0.3 |
| CAREZYME?5T | ????0.1 | ????0.2 | ????0.2 | ????0.3 |
| Sodium peroxoborate | ????-- | ????-- | ????3 | ????5 |
| Nonanoyl oxygen base benzene sulfonate | ????-- | ????-- | ????2 | ????3 |
| Optical white 2(ppm) | ????0.005 | ????0.01 | ????-- | ????-- |
| Optical white 3(ppm) | ????-- | ????-- | ????0.008 | ????0.01 |
| Minor component/filler | Balance | Balance | Balance | Balance |
1. according to the stain remover polymkeric substance of US4968451 Scheibel etc.
2. according to the phthalocyanine and the naphthalene cyanines-two [poly-(ethylene glycol 350) methyl ether] of photobleaching silicon (IV) (1: the 3) ratio of embodiment 11.
3. according to the phthalocyanine and naphthalene cyanines-two (Neodol 23-6.5) methyl ether of photobleaching silicon (IV) (1: the 3) ratio of embodiment 11).
Embodiment 17～20
Weight %
| Component | ????17 | ????18 | ????19 | ????20 |
| C 12-C 14Alkyl sulfuric ester | ????6 | ????6 | ????8 | ????7 |
| C 12-C 14Alkyl ethoxylates (EO4.2) | ????11 | ????12 | ????10 | ????5 |
| Zeolite | ????38 | ????35 | ????30 | ????10 |
| Trisodium citrate | ????-- | ????-- | ????-- | ????2 |
| SKS-6 silicate auxiliary agent | ????-- | ????-- | ????-- | ????10 |
| Acrylate/maleate copolymer | ????-- | ????-- | ????-- | ????4 |
| Yellow soda ash | ????9 | ????10 | ????4 | ????5 |
| EDTMP 1 | ????0.2 | ????-- | ????0.3 | ????-- |
| Ethylenediamine disuccinate | ????-- | ????-- | ????-- | ????0.4 |
| SPC-D | ????8 | ????-- | ????10 | ????25 |
| Nonanoyl oxygen base benzene sulfonate | ????-- | ????-- | ????3 | ????-- |
| Tetra acetyl ethylene diamine | ????7 | ????-- | ????-- | ????-- |
| Savinase(4.0KNPU/g) | ????2 | ????1.5 | ????2 | ????1.5 |
| Lipolase(100000LU/g) | ????0.2 | ????0.5 | ????0.5 | ????-- |
| Soap | ????1 | ????-- | ????-- | ????-- |
| Froth suppressor | ????2 | ????2 | ????2 | ????2 |
| Stain remover 2 | ????0.5 | ????-- | ????0.5 | ????-- |
| Stain remover 3 | ????0.5 | ????0.5 | ????-- | ????0.5 |
| Dispersion agent 4 | ????-- | ????2.5 | ????-- | ????-- |
| Optical white 5(ppm) | ????0.005 | ????0.01 | ????-- | ????-- |
| Optical white 6(ppm) | ????-- | ????-- | ????0.008 | ????0.01 |
| Minor component/filler | Balance | Balance | Balance | Balance |
1. ethylenediamine tetramethylene phosphonic acid ester.
2. according to US5415807, Grosselink etc., the stain remover polymkeric substance in May 16 nineteen ninety-five.
3. according to US4702857, Grosselink etc., the stain remover polymkeric substance on October 27th, 1987.
4. according to US5565145, Watson etc., the hydrophobic dirt dispersant on October 15th, 1996.
5. the optical white of embodiment 12.
6. according to the phthalocyanine and the naphthalene cyanines-two [glycerine-two-(Diethylene Glycol methyl ether)] of photobleaching silicon (IV) (1: the 3) ratio of embodiment 11.
Embodiment 21
| Component | Weight % |
| C 12Linear alkyl benzene sulfonate | ????30 |
| Phosphoric acid salt (as tripoly phosphate sodium STPP) | ????7 |
| Yellow soda ash | ????15 |
| Trisodium phosphate | ????7 |
| The coconut single ethanol amide | ????2 |
| Zeolite A | ????5 |
| Carboxymethyl cellulose | ????0.2 |
| Polyacrylic ester (m.w.1400) | ????0.2 |
| SPC-D | ????15 |
| Proteolytic enzyme | ????0.3 |
| CaSO 4 | ????1 |
| MgSO 4 | ????1 |
| Optical white 1(ppm) | ????0.01 |
| Minor component/filler | Balance |
1. the SYNTHETIC OPTICAL WHITNER of embodiment 12
Low aqueous cleaning compositions
Embodiment 22
| Component | Weight % |
| Optical white 1(ppm) | ????0.005-1.5 |
| BPP 2 | ????5-25 |
| 1, the 2-ethohexadiol | ????0.1-70 |
| Alkyl ethoxyquin (E1) sal epsom | ????0.01-0.8 |
| Alkyl ethoxyquin (E6.5) sal epsom | ????0.01-0.8 |
| C 12The dimethyl amine oxide compound | ????0.01-0.8 |
| PEMULEN 3 | ????0.05-0.2 |
| Spices | ????0.01-1.5 |
| Water | Balance |
1. the optical white of embodiment 11
2. other cosolvent, it can be used from the present invention together with the BPP that comprises various glycol ethers, MPP, EPP and PPP primary solvent one, comprise with trade(brand)name, as commercially available materials such as Carbitol, methyl Carbitol, butyl Carbitol, propyl group Carbitol, hexyl Cellosolve.If desired and because the security and the smell of family's service requirements can use various conventional muriates and hydrocarbon exsiccant cleaning solvent.Comprising 1,2-ethylene dichloride, trieline, different paraffin and their mixture.
3. as disclosed in US4758641 and 5004557, this class polyacrylic ester comprises it can being the crosslinked and noncrosslinking homopolymer of various degree.Preferred the present invention is that molecular weight is about 100000 to about 10000000, preferred 2000000 to 5000000 homopolymer.
For disclosed material among the embodiment 29, adopt any non-impregnated technology and every kilogram of fabric that will clean about 5 to about 50 cleaning compositions that restrain, can guarantee good clean-up performance.Adopt the polyacrylic ester emulsifying agent of said lower concentration can reduce residual on fabric.
Adopt above-mentioned composition washing fabric, general consumption arrives about 10000ppm for about 10ppm.Fabric is being had drying under the situation of light, and the sunlight of preferred nature is to obtain improved photobleaching effect.
Claims (13)
1. the metal cyanines photosensitive mixtures of a hydridization, this mixture contains one or several hybrid compounds with following general formula:
Wherein every kind of this mixture metal cyanines contain:
A) photolytic activity metal or nonmetal M, wherein said photolytic activity metal or nonmetal M are selected from silicon, germanium, tin, lead, aluminium, platinum, palladium, phosphorus and their mixture, and condition is that said metal or nonmetallic valency are 3 or 4;
B) aromatic nucleus A, B, C and D, wherein each ring be selected from replacement respectively or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, anthracene, phenanthrene and their mixture; With
C) the axial R unit of adjusting solubleness and weather resistance; The value of t is 1 or 2;
Condition is that the Q band maximum absorption wavelength scope of every kind of photosensitizers of said mixture is 600 nanometers or bigger.
2. the compound of claim 1, wherein photosensitizers cyanines ring contains:
A) phenyl ring unit, general formula is as follows:
Or
B) 2, the inferior naphthalene nucleus of 3-unit, general formula is as follows:
Or
C) 1, the inferior naphthalene nucleus of 2-unit, general formula is as follows:
Or
D) anthracene nucleus unit, general formula:
With
E) phenanthrene ring unit, general formula is as follows:
Or
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit is selected from respectively:
A) hydrogen;
B) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
G) halo C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) C of poly-hydroxy replacement
3-C
22Alkyl;
I) C
1-C
22Alkoxyl group;
J) alkoxyl group of collateralization, general formula is as follows:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H ,-OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can be respectively 0 to 6 value; Z can have 0 to 100 value respectively;
K) aryl of Qu Daiing, unsubstituted aryl or their mixture;
L) alkylidene aryl of Qu Daiing, unsubstituting alkylidene aryl or their mixture;
M) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
N) the oxyalkylene aryl of Qu Daiing, unsubstituted oxyalkylene aryl or their mixture;
O) the alkylene oxide group aryl of Qu Daiing and unsubstituted alkylene oxide group aryl or their mixture;
P) C
1-C
22Alkylthio, C
3-C
22The alkylthio of side chain or their mixture;
Q) ester units, general formula is-CO
2R
25, R wherein
25Be
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
Ii) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
The iii) C that replaces of poly-hydroxy
3-C
22Alkylidene group;
Iv) C
3-C
22Glycol;
V) C
1-C
22Alkoxyl group;
Vi) C
3-C
22The alkoxyl group of collateralization;
The vii) aryl of Qu Daiing, unsubstituted aryl, perhaps their mixture;
The viii) alkylidene aryl of Qu Daiing, unsubstituted alkylidene aryl or their mixture;
Ix) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
X) the oxyalkylene aryl of Qu Daiing, unsubstituted oxyalkylene aryl, perhaps their mixture;
Xi) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
R) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture; R
28Be:
I) hydrogen;
Ii) C
1-C
22Alkyl, C
3-C
22The alkylidene group of collateralization, C
2-C
22Alkylene group, C
3-C
22The alkylene group of collateralization and their mixture;
A is nitrogen or oxygen, and X is chlorine, bromine, iodine or other water soluble anion, and v is 0 or 1, and u is 0 to 22;
S) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl and their mixture;
T) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is:
I) hydrogen;
Ii) hydroxyl;
iii)-CO
2H；
iv)-SO
3 -M
+；
v)-OSO
3 -M
+；
Vi) C
1-C
6Alkoxyl group;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Ix) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12.
U) siloxy-of Qu Daiing, general formula is as follows:
-OSiR
31R
32R
33
R wherein
31, R
32And R
33Be selected from respectively:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
The ii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The iii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Iv) alkyl inferior ethoxyl unit, its general formula is:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is
A) hydrogen;
B) hydroxyl;
c)-CO
2H；
d)-SO
3 -M
+；
e)-OSO
3 -M
+；
F) C
1-C
6Alkoxyl group;
G) aryl of Qu Daiing, unsubstituted aryl or their mixture;
H) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
I) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12, perhaps their mixture; With their mixture.
3. claim 1 or 2 compound, wherein axially the R unit comprises respectively:
A) hydrogen;
B) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
G) C of halogen replacement
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) C of poly-hydroxy replacement
3-C
22Alkyl;
I) C
1-C
22Alkoxyl group;
J) alkoxyl group of collateralization, general formula is as follows:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H ,-OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively; Z can have 0 to 100 value respectively;
K) aryl of Qu Daiing, unsubstituted aryl or their mixture;
L) alkylidene aryl of Qu Daiing, unsubstituting alkylidene aryl or their mixture;
M) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
N) the oxyalkylene aryl of Qu Daiing, do not replace oxyalkylene aryl or their mixture;
O) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
P) C
1-C
22Alkylthio, C
3-C
22The alkylthio of side chain or their mixture;
Q) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture; R
28Be:
I) hydrogen;
Ii) C
1-C
22Alkyl, C
3-C
22The alkylidene group of collateralization, C
2-C
22Alkylene group, C
3-C
22The alkylene group of collateralization and their mixture;
A is nitrogen or oxygen, and X is chlorine, bromine, iodine or other water soluble anion, and v is 0 or 1, and u is 0 to 22;
R) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl and their mixture;
S) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is:
I) hydrogen;
Ii) hydroxyl;
iii)-CO
2H；
iv)-SO
3 -M
+；
v)-OSO
3 -M
+；
Vi) C
1-C
6Alkoxyl group;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Ix) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12.
T) hydroxy-acid group, general formula is as follows:
R wherein
37Be:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
Ii) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
The iii) C that replaces of poly-hydroxy
3-C
22Alkylidene group;
Iv) C
3-C
22Glycol;
V) C
1-C
22Alkoxyl group;
Vi) C
3-C
22The alkoxyl group of collateralization;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) alkylidene aryl of Qu Daiing, unsubstituted alkylidene aryl or their mixture;
Ix) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
X) the oxyalkylene aryl of Qu Daiing, unsubstituted oxyalkylene aryl, perhaps their mixture;
Xi) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
U) siloxy-of Qu Daiing, general formula is as follows:
-OSiR
31R
32R
33R wherein
31, R
32And R
33Be selected from respectively:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
The ii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The iii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Iv) alkyl inferior ethoxyl unit, its general formula is:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is
A) hydrogen;
B) hydroxyl;
c)-CO
2H；
d)-SO
3 -M
+；
e)-OSO
3 -M
+；
F) C
1-C
6Alkoxyl group;
G) aryl of Qu Daiing, unsubstituted aryl or their mixture;
H) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
I) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12, perhaps their mixture; With their mixture.
4. the compound of claim 1～3, wherein axially the R unit has following general formula:
-Y
i-L
jOr-Y
i-Q
jWherein Y is selected from O, CR
41R
42, OSiR
41R
42, OSnR
41R
42With their connection portion of mixture; R wherein
41And R
42Be hydrogen, C
1-C
4Alkyl, halogen and their mixture; I is 0 or 1, and j is 1 to 3;
L is a ligand, is selected from:
A) C
3-C
30Linear alkyl, C
3-C
30Collateralization alkyl, C
2-C
30Linear chain thiazolinyl, C
3-C
30Collateralization alkenyl, C
6-C
20Aryl, C
7-C
20Arylalkyl, C
7-C
20Alkylaryl;
B) alkyl inferior ethoxyl unit, general formula is:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
1-C
20Alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20The alkenyl of collateralization, C
6-C
20Aryl, C
7-C
30Arylalkyl, C
6-C
20Alkylaryl; R
38Be selected from C
1-C
4Linear alkylene, C
3-C
4The alkylidene group of collateralization, C
3-C
6Hydroxy alkylidene and their mixture; R
39Be selected from C
2-C
20Alkylidene group, C
6-C
20The alkylidene group of collateralization, C
7-C
20Arylidene, C
7-C
30Aryl alkylene, C
7-C
30Alkyl arylene; X from 1 to 100; Y is 0 or 1; With
C) its mixture;
Q is the ion part, and general formula is as follows:
-R
40-P is R wherein
40Be selected from C
3-C
30Linear alkylene, C
3-C
30The alkylidene group of collateralization, C
2-C
30Linear alkylene group, C
3-C
30The alkylene group of collateralization, C
6-C
16Arylidene and their mixture; P is selected from-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M
+,-OPO
3 2-M
+,-N
+(R
36)
3X
-R
36Independently be hydrogen, C
1-C
6Alkyl ,-(CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; M is the water-soluble cationic that electroneutral enough electric charges can be provided, and X is a water soluble anion.
5. the compound of claim 1～4, wherein hydrophobic axial R unit is alkyl inferior ethoxyl unit, general formula is as follows:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
3-C
20Linear alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20Collateralization alkenyl, C
6-C
10Aryl or their mixture, preferred hydrogen, C
1-C
20Alkyl, C
3-C
20The alkyl of collateralization, C
5-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Alkylaryl, more preferably hydrogen, C
1-C
20Alkyl or C
3-C
20The alkyl of collateralization, most preferably hydrogen or methyl; R
38Be selected from C
1-C
4Linear alkylene, C
1-C
4Collateralization alkylidene group and their mixture, preferred C
1-C
4Linear alkylene; R
39Be selected from C
1-C
6Alkylidene group, C
1-C
6The alkylidene group of collateralization, C
6-C
10Arylidene and their mixture; X from 1 to 50; Y is 0 or 1, preferred 0.
6. the compound of claim 1～5, wherein R
1-R
8Be hydrogen, halogen, C
1-C
22Alkoxyl group and their mixture, preferred hydrogen, bromine, iodine, methoxyl group.
7. photo bleach compositions, contain:
A) 0.001ppm at least, preferred 0.01 to 10000ppm, more preferably 0.1 to 5000ppm, most preferably 10 to the hybridized metal cyanines photosensitive mixtures of 1000ppm, this mixture contains two kinds or more of, preferred about 3 to 100 kinds, more preferably 10 to 100 kinds have below the hybrid compounds of general formula:
Wherein every kind of this mixture metal cyanines contain:
A) photolytic activity metal or nonmetal M, wherein said photolytic activity metal or nonmetal M are selected from silicon, germanium, tin, lead, aluminium, platinum, palladium, phosphorus and their compound, and condition is that said metal or nonmetallic valency are 3 or 4;
B) aromatic nucleus A, B, C and D, wherein each ring be selected from replacement respectively or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, anthracene, phenanthrene and their mixture; With
C) the axial R unit of adjusting solubleness and weather resistance; The value of t is 1 or 2;
Condition is that the Q band maximum absorption wavelength scope of every kind of photosensitizers of said mixture is 600 nanometers or bigger.
B) at least 0.1%, preferred 0.1% to 30%, more preferably 1% to 30%, the detergent surfactant of 5% to 20% weight most preferably, said detergent surfactant is selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion, amphoterics and their mixture;
C) balance carrier and other binder component, said binder component is selected from buffer reagent, auxiliary agent, sequestrant, filling salt, stain remover, dispersion agent, enzyme, enzyme promotor, spices, thickening material, clay, SYNTHETIC OPTICAL WHITNER, solvent and their mixture.
8. the composition of claim 7, wherein photosensitizers cyanines ring contains:
A) phenyl ring unit, general formula is as follows:
Or
B) 2, the inferior naphthalene nucleus of 3-unit, general formula is as follows:
Or
C) 1, the inferior naphthalene nucleus of 2-unit, general formula is as follows:
Or
D) anthracene nucleus unit, general formula:
With
E) phenanthrene ring unit, general formula is as follows:
Or
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit is selected from respectively:
A) hydrogen;
B) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
G) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) C of poly-hydroxy replacement
3-C
22Alkyl;
I) C
1-C
22Alkoxyl group;
J) alkoxyl group of collateralization, general formula is as follows:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H ,-OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively; Z can have 0 to 100 value respectively;
K) aryl of Qu Daiing, unsubstituted aryl or their mixture;
L) alkylidene aryl of Qu Daiing, unsubstituting alkylidene aryl or their mixture;
M) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
N) the oxyalkylene aryl of Qu Daiing, do not replace oxyalkylene aryl or their mixture;
O) the alkylene oxide group aryl of Qu Daiing and unsubstituted alkylene oxide group aryl or their mixture;
P) C
1-C
22Alkylthio, C
3-C
22The alkylthio of collateralization or their mixture;
Q) ester units, general formula is-CO
2R
25, R wherein
25Be
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
Ii) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
The iii) C that replaces of poly-hydroxy
3-C
22Alkylidene group;
Iv) C
3-C
22Glycol;
V) C
1-C
22Alkoxyl group;
Vi) C
3-C
22The alkoxyl group of collateralization;
The vii) aryl of Qu Daiing, unsubstituted aryl, perhaps their mixture;
The viii) alkylidene aryl of Qu Daiing, unsubstituted alkylidene aryl or their mixture;
Ix) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
X) the oxyalkylene aryl of Qu Daiing, the oxyalkylene aryl that replaces, perhaps their mixture;
Xi) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
R) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture; R
28Be:
I) hydrogen;
Ii) C
1-C
22Alkyl, C
3-C
22The alkylidene group of collateralization, C
2-C
22Alkylene group, C
3-C
22The alkylene group of collateralization or their mixture;
A is nitrogen or oxygen, and X is chlorine, bromine, iodine or other water soluble anion, and v is 0 or 1, and u is 0 to 22;
S) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture;
T) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is:
I) hydrogen;
Ii) hydroxyl;
iii)-CO
2H；
iv)-SO
3 -M
+；
v)-OSO
3 -M
+；
Vi) C
1-C
6Alkoxyl group;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Ix) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12.
U) siloxy-of Qu Daiing, general formula is as follows:
-OSiR
31R
32R
33
R wherein
31, R
32And R
33Be selected from respectively:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
The ii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The iii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Iv) alkyl inferior ethoxyl unit, its general formula is:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is
A) hydrogen;
B) hydroxyl;
c)-CO
2H；
d)-SO
3 -M
+；
e)-OSO
3 -M
+；
F) C
1-C
6Alkoxyl group;
G) aryl of Qu Daiing, unsubstituted aryl or their mixture;
H) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
I) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12, perhaps their mixture; With their mixture.
9. claim 7 or 8 composition, wherein axially the R unit comprises respectively:
A) hydrogen;
H) halogen;
C) hydroxyl;
D) cyano group;
E) nitrilo;
F) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
G) C of halogen replacement
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
H) C of poly-hydroxy replacement
3-C
22Alkyl;
I) C
1-C
22Alkoxyl group;
J) alkoxyl group of collateralization, general formula is as follows:
Or
Wherein B is hydrogen, hydroxyl, C
1-C
30Alkyl, C
1-C
30Alkoxyl group ,-CO
2H ,-OCH
2CO
2H ,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M ,-OPO
3 2-M and their mixture; M is the water-soluble cationic that satisfies charge balance with capacity; X is 0 or 1, and y can have 0 to 6 value respectively; Z can have 0 to 100 value respectively;
K) aryl of Qu Daiing, unsubstituted aryl or their mixture;
L) alkylidene aryl of Qu Daiing, unsubstituting alkylidene aryl or their mixture;
M) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
N) the oxyalkylene aryl of Qu Daiing, do not replace oxyalkylene aryl or their mixture;
O) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
P) C
1-C
22Alkylthio, C
3-C
22The alkylthio of side chain or their mixture;
Q) alkylidene amino unit, general formula is as follows:
R wherein
26And R
27Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture;
R
28Be:
I) hydrogen;
Ii) C
1-C
22Alkyl, C
3-C
22The alkylidene group of collateralization, C
2-C
22Alkylene group, C
3-C
22The alkylene group of collateralization or their mixture;
A is nitrogen or oxygen, and X is chlorine, bromine, iodine or other water soluble anion, and v is 0 or 1, and u is 0 to 22;
R) amino unit, general formula is as follows:
-NR
29R
30R wherein
29And R
30Be C
1-C
22Alkyl, C
3-C
22Collateralization alkyl, C
2-C
22Alkenyl, C
3-C
22Collateralization alkenyl or their mixture;
S) alkyl inferior ethoxyl unit, general formula is as follows:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is:
I) hydrogen;
Ii) hydroxyl;
iii)-CO
2H；
iv)-SO
3 -M
+；
v)-OSO
3 -M
+；
Vi) C
1-C
6Alkoxyl group;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Ix) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12.
T) hydroxy-acid group, general formula is as follows:
R wherein
37Be:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
Ii) halogenated C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization, perhaps their mixture;
The iii) C that replaces of poly-hydroxy
3-C
22Alkylidene group;
Iv) C
3-C
22Glycol;
V) C
1-C
22Alkoxyl group;
Vi) C
3-C
22The alkoxyl group of collateralization;
The vii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The viii) alkylidene aryl of Qu Daiing, unsubstituted alkylidene aryl or their mixture;
Ix) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
X) the oxyalkylene aryl of Qu Daiing, unsubstituted oxyalkylene aryl, perhaps their mixture;
Xi) the alkylene oxide group aryl of Qu Daiing, unsubstituted alkylene oxide group aryl or their mixture;
U) siloxy-of Qu Daiing, general formula is as follows:
-OSiR
31R
32R
33R wherein
31, R
32And R
33Be selected from respectively:
I) C
1-C
22Alkyl, C
3-C
22The alkyl of collateralization, C
2-C
22Alkenyl, C
3-C
22The alkenyl of collateralization or their mixture;
The ii) aryl of Qu Daiing, unsubstituted aryl or their mixture;
The iii) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
Iv) alkyl inferior ethoxyl unit, its general formula is:
-(A)
v-(CH
2)
y(OCH
2CH
2)
xZ
Wherein Z is
A) hydrogen;
B) hydroxyl;
c)-CO
2H；
d)-SO
3 -M
+；
e)-OSO
3 -M
+；
F) C
1-C
6Alkoxyl group;
G) aryl of Qu Daiing, unsubstituted aryl or their mixture;
H) aryloxy of Qu Daiing, unsubstituted aryloxy or their mixture;
I) alkylidene amino or their mixture;
A is nitrogen or oxygen, and M is a water-soluble cationic, and v is 0 or 1, and x is 0 to 100, and y is 0 to 12, perhaps their mixture; With their mixture.
10. the composition of claim 7～9, wherein axially the R unit has following general formula:
-Y
i-L
jOr-Y
i-Q
jWherein Y is selected from O, CR
41R
42, OSiR
41R
42, OSnR
41R
42With their connection portion of mixture; R wherein
41And R
42Be hydrogen, C
1-C
4Alkyl, halogen and their mixture; I is 0 or 1, and j is 1 to 3;
L is a ligand, is selected from:
A) C
3-C
30Linear alkyl, C
3-C
30Collateralization alkyl, C
2-C
30Linear chain thiazolinyl, C
3-C
30Collateralization alkenyl, C
6-C
20Aryl, C
7-C
20Arylalkyl, C
7-C
20Alkylaryl;
B) alkyl inferior ethoxyl unit, general formula is:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
1-C
20Alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20The alkenyl of collateralization, C
6-C
20Aryl, C
7-C
30Arylalkyl, C
6-C
20Alkylaryl; R
38Be selected from C
1-C
4Linear alkylene, C
3-C
4The alkylidene group of collateralization, C
3-C
6Hydroxy alkylidene and their mixture; R
39Be selected from C
2-C
20Alkylidene group, C
6-C
20The alkylidene group of collateralization, C
7-C
20Arylidene, C
7-C
30Aryl alkylene, C
7-C
30Alkyl arylene; X from 1 to 100; Y is 0 or 1; With
C) its mixture;
Q is the ion part, and general formula is as follows:
-R
40-P is R wherein
40Be selected from C
3-C
30Linear alkylene, C
3-C
30The alkylidene group of collateralization, C
2-C
30Linear alkylene group, C
3-C
30The alkylene group of collateralization, C
6-C
16Arylidene and their mixture; P is selected from-CO
2 -M
+,-SO
3 -M
+,-OSO
3 -M
+,-PO
3 2-M
+,-OPO
3 -M
+,-N
+(R
36)
3X
-R
36Be hydrogen, C
1-C
6Alkyl ,-(CH
2)
nOH ,-(CH
2CH
2O)
nH and their mixture; Wherein n is 1 to 4; M is the water-soluble cationic that electroneutral enough electric charges can be provided, and X is a water soluble anion.
11. the composition of claim 7～10, wherein the axial R of hydrophobicity unit is alkyl inferior ethoxyl unit, and general formula is as follows:
-(R
39)
y(OR
38)
xOZ wherein Z is selected from hydrogen, C
3-C
20Linear alkyl, C
3-C
20Collateralization alkyl, C
2-C
20Linear chain thiazolinyl, C
3-C
20Collateralization alkenyl, C
6-C
10Aryl or their mixture, preferred hydrogen, C
1-C
20Alkyl, C
3-C
20The alkyl of collateralization, C
5-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Alkylaryl, more preferably hydrogen, C
1-C
20Alkyl or C
3-C
20The alkyl of collateralization, most preferably hydrogen or methyl; R
38Be selected from C
1-C
4Linear alkylene, C
1-C
4Collateralization alkylidene group and their mixture, preferred C
1-C
4Linear alkylene; R
39Be selected from C
1-C
6Alkylidene group, C
1-C
6The alkylidene group of collateralization, C
6-C
10Arylidene and their mixture; X from 1 to 50; Y is 0 or 1, preferred 0.
12. any one composition, wherein R in the claim 8～11
1～R
8Be hydrogen, halogen, C
1-C
22Alkoxyl group and their mixture, preferred hydrogen, bromine, iodine, methoxyl group.
13. method of cleaning dirty fabric, comprise that the aqueous cleaning solution of any photosensitive composition of the claim 1～6 of 0.001ppm contacts the dirty fabric that needs are cleaned with containing at least, the surface of the fabric that will handle is exposed to the light source that minimum wavelength is 300～1200 nanometers again.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3354997P | 1997-01-24 | 1997-01-24 | |
| US60/033,549 | 1997-01-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1260829A true CN1260829A (en) | 2000-07-19 |
Family
ID=21871058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98803338A Pending CN1260829A (en) | 1997-01-24 | 1998-01-22 | Photobleaching compositions comprising mixed metallocyanines |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6413924B2 (en) |
| EP (1) | EP0960184B1 (en) |
| JP (1) | JP2001511198A (en) |
| CN (1) | CN1260829A (en) |
| AT (1) | ATE237668T1 (en) |
| BR (1) | BR9807510A (en) |
| CA (1) | CA2277934A1 (en) |
| DE (1) | DE69813514D1 (en) |
| MA (1) | MA24457A1 (en) |
| WO (1) | WO1998032826A2 (en) |
| ZA (1) | ZA98530B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940093A (en) * | 2014-01-31 | 2016-09-14 | 巴斯夫欧洲公司 | Use of ortho-substituted ethoxylated Al or Zn-phthalocyanine compounds as photobleach agents in laundry detergents |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9917226A (en) * | 1999-03-05 | 2002-02-26 | Procter & Gamble | Composition comprising a photo-oxidation agent and uses of the agent |
| US6462008B1 (en) * | 1999-03-05 | 2002-10-08 | Case Western Reserve University | Detergent compositions comprising photobleaching delivery systems |
| AU3509200A (en) * | 1999-03-05 | 2000-09-21 | Case Western Reserve University | Consumer product compositions comprising photosensitive materials as photobleaches or photodisinfectants |
| AU3507900A (en) * | 1999-03-05 | 2000-09-21 | Case Western Reserve University | Hydrophobic liquid photobleaches |
| GB2359560B (en) | 1999-12-22 | 2002-03-20 | Reckitt Benckiser | Photocatalytic cleaning compositions, atricles and methods |
| GB9930248D0 (en) * | 1999-12-22 | 2000-02-09 | Johnson Matthey Plc | Surface cleaner |
| US7345016B2 (en) * | 2003-06-27 | 2008-03-18 | The Procter & Gamble Company | Photo bleach lipophilic fluid cleaning compositions |
| US9834740B2 (en) * | 2014-01-24 | 2017-12-05 | The Procter & Gamble Company | Photoactivators |
| DE102021213793A1 (en) | 2021-12-03 | 2023-06-07 | Henkel Ag & Co. Kgaa | N-substituted 2-(6-hydroxy-3-oxo-3H-xanthen-9-yl)benzamides as photoactivators in detergents |
| DE102021213788A1 (en) | 2021-12-03 | 2023-06-07 | Henkel Ag & Co. Kgaa | Anthracene-9,10-dione derivatives as photoactivators in detergents |
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| US3094536A (en) | 1961-01-03 | 1963-06-18 | Malcolm E Kenney | Silicon phthalocyanines |
| GB1408144A (en) | 1972-06-02 | 1975-10-01 | Procter & Gamble Ltd | Bleaching process |
| GB1372035A (en) | 1971-05-12 | 1974-10-30 | Procter & Gamble Ltd | Bleaching process |
| US4033718A (en) | 1973-11-27 | 1977-07-05 | The Procter & Gamble Company | Photoactivated bleaching process |
| CH630127A5 (en) * | 1977-03-25 | 1982-05-28 | Ciba Geigy Ag | METHOD FOR BLEACHING TEXTILES. |
| FR2387658A1 (en) | 1977-03-25 | 1978-11-17 | Ciba Geigy Ag | PROCEDURE FOR FIGHTING MICROORGANISMS |
| CA1128258A (en) | 1978-01-11 | 1982-07-27 | Nabil Y. Sakkab | Composition for combined washing and bleaching of fabrics |
| EP0003371A1 (en) | 1978-01-11 | 1979-08-08 | THE PROCTER & GAMBLE COMPANY | Composition containing a cationic substance and a photoactivator for improved washing and bleaching of fabrics |
| CA1104451A (en) | 1978-02-28 | 1981-07-07 | Manuel Juan De Luque | Detergent bleach composition and process |
| MX155643A (en) | 1980-02-29 | 1988-04-11 | Ciba Geigy Ag | FABRIC WHITENING COMPOSITION |
| EP0054992B1 (en) * | 1980-12-22 | 1985-03-20 | Unilever N.V. | Composition containing a photo-activator for improved bleaching |
| US4497741A (en) | 1981-12-09 | 1985-02-05 | Ciba-Geigy Corporation | Water-soluble zinc and aluminium phthalocyanines |
| GR78065B (en) * | 1982-02-19 | 1984-09-26 | Unilever Nv | |
| CH657864A5 (en) * | 1984-02-17 | 1986-09-30 | Ciba Geigy Ag | WATER-SOLUBLE PHTHALOCYANINE COMPOUNDS AND THE USE THEREOF AS PHOTOACTIVATORS. |
| CH658771A5 (en) | 1984-05-28 | 1986-12-15 | Ciba Geigy Ag | AZAPHTHALOCYANINE AND THEIR USE AS PHOTOACTIVATORS. |
| DE3711762A1 (en) | 1987-04-07 | 1988-10-27 | Basf Ag | MIXED PHTHALO-NAPHTHALOCYANINE AND THIN RADIATION-SENSITIVE COATING FILMS CONTAINING THESE COMPOUNDS |
| JPH02202482A (en) | 1989-02-01 | 1990-08-10 | Mitsui Petrochem Ind Ltd | Optical recording medium |
| ES2163393T3 (en) | 1990-05-15 | 2002-02-01 | Hyperion Inc | FLUORESCENT PORFIRINA AND FLUORESCENT FTALOCIANINE - DERIVATIVES OF POLYETHYLENE GLYCOL, POLYOL AND SACARIDS AS FLUORESCENT PROBES. |
| ATE146508T1 (en) | 1990-11-02 | 1997-01-15 | Zeneca Ltd | POLYSUBSTITUTED PHTHALOCYANINES |
| JP2871898B2 (en) * | 1991-06-06 | 1999-03-17 | 三菱製紙株式会社 | Germanium phthalocyanine-based photoelectric conversion agent |
| JPH0673397A (en) | 1992-08-27 | 1994-03-15 | Nippon Shokubai Co Ltd | New photoactivator, new bleaching agent, and new microbicide |
| DE4230655A1 (en) * | 1992-09-14 | 1994-03-17 | Ciba Geigy | Process for improving the whiteness, brightness and color location of fibrous materials |
| US5679661A (en) * | 1995-07-25 | 1997-10-21 | The Procter & Gamble Company | Low hue photodisinfectants |
| US5916481A (en) * | 1995-07-25 | 1999-06-29 | The Procter & Gamble Company | Low hue photobleaches |
| GB2313122A (en) * | 1996-05-18 | 1997-11-19 | Zeneca Ltd | Preparation of silicon-containing phthalocyanines |
-
1998
- 1998-01-22 CA CA002277934A patent/CA2277934A1/en not_active Abandoned
- 1998-01-22 CN CN98803338A patent/CN1260829A/en active Pending
- 1998-01-22 BR BR9807510A patent/BR9807510A/en unknown
- 1998-01-22 AT AT98903383T patent/ATE237668T1/en not_active IP Right Cessation
- 1998-01-22 US US09/355,153 patent/US6413924B2/en not_active Expired - Fee Related
- 1998-01-22 JP JP53199898A patent/JP2001511198A/en active Pending
- 1998-01-22 ZA ZA98530A patent/ZA98530B/en unknown
- 1998-01-22 DE DE69813514T patent/DE69813514D1/en not_active Expired - Lifetime
- 1998-01-22 WO PCT/US1998/000226 patent/WO1998032826A2/en active IP Right Grant
- 1998-01-22 EP EP98903383A patent/EP0960184B1/en not_active Expired - Lifetime
- 1998-01-23 MA MA24941A patent/MA24457A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940093A (en) * | 2014-01-31 | 2016-09-14 | 巴斯夫欧洲公司 | Use of ortho-substituted ethoxylated Al or Zn-phthalocyanine compounds as photobleach agents in laundry detergents |
| CN105940093B (en) * | 2014-01-31 | 2019-02-15 | 巴斯夫欧洲公司 | Ethoxylation Al or the Zn- phthalocyanine compound of ortho position substitution is in laundry detergent as the purposes of optical white |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE237668T1 (en) | 2003-05-15 |
| EP0960184B1 (en) | 2003-04-16 |
| WO1998032826A3 (en) | 1998-09-11 |
| BR9807510A (en) | 2000-03-21 |
| JP2001511198A (en) | 2001-08-07 |
| US6413924B2 (en) | 2002-07-02 |
| US20010003736A1 (en) | 2001-06-14 |
| EP0960184A2 (en) | 1999-12-01 |
| MA24457A1 (en) | 1998-10-01 |
| ZA98530B (en) | 1998-07-29 |
| CA2277934A1 (en) | 1998-07-30 |
| DE69813514D1 (en) | 2003-05-22 |
| WO1998032826A2 (en) | 1998-07-30 |
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